Treatments and kits for creating renewable surface protective coatings

ABSTRACT

Methods, treatment compositions and treatment systems for forming a detachable and renewable coating on a receptive surface by a process of applying a treatment composition comprising a plurality of hydrophobically modified fumed silica particles colloidally dispersed in a volatile solvent; allowing the volatile solvent to evaporate; and thereby depositing a protective coating on the receptive surface consisting of a layer of the hydrophobically modified particles. The process provides a coating with dirt- and water-repellency properties that effectively shed dry particulate soils as well as water from the treated receptive surface. The methods, treatment compositions and treatment systems are useful in providing detachable coatings and treated articles featuring surface protective benefits including dirt- and water-repellency, self-cleaning with water, and easier cleaning benefits when applied to a variety of automotive and home surfaces, both interior and exterior.

CROSS REFERENCE TO RELATED APPLICATIONS

The present application is a continuation-in-part of copendingapplication Ser. No. 12/941,669, filed Nov. 8, 2010, which is acontinuation of U.S. application Ser. No. 11/264,606 filed Oct. 31,2005, now U.S. Pat. No. 7,828,889, which is a continuation-in-part ofU.S. application Ser. No. 10/740,346, filed Dec. 18, 2003, now U.S. Pat.No. 7,083,828, which is incorporated herein by reference in itsentirety.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to methods, treatment compositions andtreatment systems for forming detachable and renewable protectivecoatings on a receptive surface by a process of applying to thereceptive surface a treatment composition comprising a plurality ofhydrophobic particles colloidally dispersed in a volatile solvent;allowing the volatile solvent to evaporate; and thereby depositing acoating on the receptive surface that provides dirt- and water-repellentproperties, self-cleaning and easier next time cleaning benefits.

2. Description of the Related Art

The principle of self-cleaning coatings is well known in the literature.The effect generally requires two essential features: one being ahydrophobic surface or hydrophobic coating on a surface; and the secondbeing some degree of surface roughness which combine to produce astructured “superhydrophobic” surface, exhibiting high water contactangles that act to readily repel water and shed adherent particulatesoils with even small amounts of water alone, without requiring the useof typical cleaning agents.

The use of hydrophobic materials, such as perfluorinated polymers, toproduce hydrophobic surfaces is known. A further development of thesesurfaces consists in structuring the surfaces in the μm to nm range.U.S. Pat. No. 5,599,489 discloses a process in which a surface can berendered particularly repellent by bombardment with particles ofappropriate size, followed by perfluorination.

A suitable combination of structure and hydrophobic properties permitseven small amounts of water moving on the surface to entrain adherentdirt particles and clean the surface (see, for example, U.S. Pat. No.6,660,363; U.S. Pat. No. 3,354,022). The prior art of EP-B-0 933 388requires an aspect ratio >1 and a surface energy of less than 20 mN/mfor these self-cleaning surfaces; the aspect ratio being defined here asthe quotient which is the ratio of the height of the structure to itswidth. The abovementioned criteria are typically found in nature, forexample, in the lotus leaf. The surface of the plant is composed of ahydrophobic waxy material and has elevations separated by a few μm.Water droplets substantially contact only the peaks of the elevations.There are many descriptions in the literature of water-repellentsurfaces of this type.

EP-A-0 909 747 teaches a process for generating a self-cleaning surface.The surface has hydrophobic elevations whose height is from 5 to 200 μm.A surface of this type is produced by applying a dispersion ofpulverulent particles and of an inert material in a siloxane solutionand then curing. The structure-forming particles are therefore securedto the surface by way of an auxiliary medium.

U.S. Pat. Pub. No. 2005/0136217A1 concludes that it is technicallypossible to render the surfaces of articles artificially self-cleaning.The surface structures necessary for this purpose, which are composed ofelevations and depressions, have a separation in the range from 0.1 to200 μm between the elevations of the surface structures, and have anelevation height in the range from 0.1 to 100 μm. The materials used forthis purpose are composed of hydrophobic polymers or of lastinglyhydrophobized material. Release of the particles from the carrier matrixhas to be prevented.

This principle has been borrowed from nature. Small contact surfaceslower the level of van der Waals interaction responsible for adhesion toflat surfaces with low surface energy. For example, the leaves of thelotus plant have elevations composed of a wax, and these reduce the areaof contact with water.

Processes for producing these structured surfaces are likewise known.Besides the use of a master template to mold these structures in fill-indetail by an injection molding or embossing processes, there are alsoknown processes that utilize the application of particles to a surface.This is disclosed, for example, in U.S. Pat. No. 5,599,489.

Recently, attempts have been made to provide self-cleaning surfaces ontextiles. It has been found that self-cleaning surfaces can be generatedby applying fine-particle SiO₂ (AEROSIL®) to textiles. In this process,the AEROSIL® materials are bonded into the polymer matrix of the textilefiber, using a solvent that partially dissolves the fiber to effectadhesion.

U.S. Pat. Pub. No. 2004/0154106A1 describes polymer fibers withself-cleaning surfaces. In the prior art disclosure, the self-cleaningsurface is obtained by exposure to a solvent, which comprisesstructure-forming particles, using the solvent to solvate the surface ofthe polymer fibers, adhesion of the structure-forming particles to thesolvated surface, and removing the solvent. The disadvantage of thisprocess is that, during processing of the polymer fibers (spinning,knitting, etc.), the structure-forming particles, and therefore thestructure that renders the surface self-cleaning, can become damaged orsometimes lost entirely, the result being that the self-cleaning effectis also lost.

U.S. Pat. Pub. No. 2005/0103457A1 describes textile sheets with aself-cleaning and water-repellent surface composed of at least onesynthetic and/or natural textile base material A, and of an artificial,at least to some extent, hydrophobic surface with elevations anddepressions composed of particles that have been securely bonded to thebase material A without adhesives, resins, or coatings. The hydrophobicsurfaces are obtained by treating the base material A with at least onesolvent that comprises the undissolved particles, and removing thesolvent, whereupon at least some of the particles become securely bondedto the surface of the base material A. However, the disadvantage of thisprior art process is the very complicated finishing of the textilesurfaces. Moreover, this prior art process requires precise matching ofthe solvent to the base material of the textiles. However, in clothingthere are generally mixed fabrics present, and this matching thereforebecomes more complicated. If the matching of the solvents is notprecise, the result can be irreparable damage to parts of the clothing.The textile surfaces therefore have to be treated prior to tailoring.

U.S. Pat. No. 6,800,354 describes substrates with a self-cleaningsurface and a process for a permanent coating of the substratesproviding the self-cleaning properties. The process includes thefollowing steps: (1) coating of the surface with a compositioncontaining structure forming particles and a layer forming material; (2)forming a cohesive layer that fixes the structure forming particlesfirmly to the surface, and then; (3) hydrophobizing the structuredsurface with a hydrophobizing agent which adheres firmly to thestructured surface. The structure forming particles preferably have anaverage diameter of less than 100 nm, more preferably in the rangebetween 5 and 50 nm. In an example, a float glass with a transparentself-cleaning surface was produced by coating the glass with acomposition by means of a screen printing process using a 100 T screen.The composition included 0.5 wt. % boric acid and 4 wt. % pyrogenicsilica with an average diameter of the primary particles of 12 nm in awater friendly medium. After drying, the coating was shock fired at 660°C. for a duration of 4 min. The hydrophobization of the structuredstoved surface was carried out by introducing an ethanolic solution oftridecafluorooctyltriethoxysilane over the surface and curing at anelevated temperature. The disadvantages of the described method is itsmultiple-step nature and the requirement of a high temperature process.In addition, it results in a permanent coating, which cannot be easilydetached by a simple cleaning procedure.

All of these coatings are characterized in that they are intended to beapplied permanently to the articles, and thus have the disadvantage thatthey cannot be simply removed and reapplied in the event of impairmentby scratching, discoloration or any other damage to the coating, surfaceor coated surface structure. If this type of damage occurs, the articleeither has to be freed from the surface structure by a complicatedmethod and retreated, or has to be disposed of if its appearance is nolonger acceptable.

U.S. Pat. Pub. No. 2005/0136217A1 describes a process for producingdetachable coatings with dirt- and water-repellent properties. Thesecoatings of the prior art are produced by spray-application ofhydrophobic alcohols, such as nonacosan-10-ol, or of alkanediols, suchas nonacosane-5,10-diol, or of waxes. The coatings of U.S. Pat. Pub. No.2005/0136217A1 can be removed from articles by strong mechanical forces,e.g. scratching, brushing, or high-pressure water treatment, or bytreatment with water which comprises detergents that disperse some ofthe structure-formers. A disadvantage of the prior art coatingsdisclosed in U.S. Pat. Pub. No. 2005/0136217A1 is the strong forcesneeded for mechanical removal of the coating. The use of strong forcesfor the mechanical removal of the coating runs the risk that when thecoating is removed the surface of the article itself will also bedamaged. Treatment with water that comprises detergents can likewiselead to damage to the article, depending on its nature.

U.S. Pat. Pub. No. 2004/0213904 describes a process for producingdetachable dirt- and water-repellent surface coatings on articles,wherein during the coating process, hydrophobic particles are applied tothe surface of the articles, thus generating a structure with elevationson the surface of the articles that has dirt- and water-repellentproperties, which comprises suspending the hydrophobic particles in asolution of an alkyl-modified silicone wax in a highly volatilesiloxane, applying this suspension to at least one surface of anarticle, and then removing the highly volatile siloxane. In thisdocument examples of compositions for producing those surface coatingsare given and procedures how they are made. The compositions aredispersions of fumed silica particles present at 1 to 2 wt. % of thetotal weight of the dispersion in a solution of an alkyl-modifiedsilicone wax present at 0.5 wt. % in decamethylcyclopentasiloxane. Theyare produced by dissolving the alkyl-modified silicone wax indecamethylcyclopentasiloxane and then dispersing the fumed silica inthis solution with vigorous stirring. Although the therein describedprocess for producing detachable dirt- and water-repellent surfacecoatings proved to provide better results with respect to run-offbehavior of water droplets and gloss values on various surfaces comparedto processes known from the prior state of the art, it still has somedisadvantages. Especially on high gloss surfaces such as glass, brushedmetal and varnished or painted surfaces the coating is easilyperceptible as a grayish or hazy layer by the naked eye which is notacceptable for many applications.

The various approaches employed in the prior art are directed tomodification of the targeted surfaces to have sufficient roughness toprovide a coating capable of exhibiting the Lotus effect, and generallyproduce non-transparent coatings and films that suffer from poor visualappearance, particularly on glossy, shiny and/or highly reflectivesurfaces. Further, approaches that provide protective coatings withimproved visual appearances rely on fixatives to firmly attach and/orembed materials onto the treated surface, accompanied by chemical,physical and/or thermal processes required to produce them and resultingin permanent and non-renewable treated articles.

It is therefore an object of the present invention to provide a method,treatment compositions and treatment systems which can produceessentially transparent protective surface coatings on a wide variety ofmaterials and form treated articles providing dirt- and water-repellencyand related surface protective benefits.

It is therefore an object of the present invention to provide a method,treatment compositions and treatment systems which can producedetachable and renewable dirt- and water-repellent surface coatings on areceptive surface, and which can also treat articles to give arelatively durable coating, which, however, can be detached using simplemeans, without requiring any chemical or physical modification or changeto the underlying substrate, which may then be readily restored to itspristine initial state when desired.

It is a further object of the present invention to provide a method,treatment compositions and treatment systems which can provide receptivesurfaces and treated articles with transparent, detachable and renewableprotective surface coatings formable on a wide variety of materials andsubstrates.

It is a further object of the present invention to provide a method,treatment compositions and treatment systems which can provide receptivesurfaces with transparent, detachable and renewable protective surfacecoatings, which can be easily renewed by removing the coatings by simplemeans and reapplying the coatings, on a wide variety of materials andsubstrates.

It is yet a further object of the present invention to provide a method,treatment compositions and treatment systems which can provide receptivesurfaces with transparent, detachable and renewable protective surfacecoatings on a wide variety of materials which thereby exhibit dirt- andwater-repellency, self-cleaning and easier next time cleaning benefits.

It is yet another object of the present invention to provide a treatmentsystem for applying and forming a protective coating on a receptivesurface using an applicator for applying a treatment composition forforming an essentially transparent, detachable and renewable protectivecoating on a receptive surface.

SUMMARY OF THE INVENTION

It was surprisingly found that detachable and renewable protectivecoatings which are substantially transparent can be applied to receptivesurfaces by use of a treatment composition containing hydrophobicallymodified silica particles, provided that said treatment composition hasbeen made by diluting, optionally while adding other functionalingredients, an initial process composition, which, in turn, has beenproduced at a high concentration of the silica, in the presence of anoptional, yet preferable disilazane derivative, and under high shearconditions. It was further surprisingly found that these protectivecoatings can exhibit good durability, even in the absence ofconventional durability agents.

In accordance with the above objects and those that will be mentionedand will become apparent below, one aspect of the present invention is amethod of forming a detachable and renewable protective coating on areceptive surface comprising the steps of (a) applying a treatmentcomposition to said receptive surface, said treatment compositioncomprising a plurality of hydrophobically modified fumed silicaparticles (to be described in greater detail hereinbelow) colloidallydispersed in a volatile solvent; (b) allowing said volatile solvent toevaporate from said receptive surface; and thereby depositing saidprotective coating on said receptive surface, wherein said protectivecoating provides dirt- and water-repellency to said receptive surface.The protective coating comprises a non-smooth coating on the receptivesurface at least after the treatment composition has been applied to thereceptive surface and has substantially dried or set. The non-smoothcoating on the receptive surface includes valleys and peaks and anaverage height between the valleys and peaks of about 1-2500 nm. Thedetachable coating can be substantially transparent and result in achange of less than 3.0 Delta E units to the receptive surface measuredbefore and after deposition of the coating.

In accordance with the above objects and those that will be mentionedand will become apparent below, one aspect of the present invention is amethod of forming a protective coating on a receptive surfacecomprising: (a) applying a treatment composition for coating a receptivesurface to said receptive surface, said treatment composition comprisinga plurality of particles colloidally dispersed in a volatile solvent;(b) allowing said volatile solvent to evaporate from said receptivesurface; and (c) depositing a detachable and renewable protectivecoating on said receptive surface, wherein said protective coatingprovides dirt- and water-repellency to said receptive surface, whereinsaid particles comprise hydrophobically modified fumed silica particleshaving a median size of between 100 and 4,000 nanometers. The protectivecoating comprises a non-smooth coating on the receptive surface at leastafter the treatment composition has been applied to the receptivesurface and has substantially dried or set. The non-smooth coating onthe receptive surface includes valleys and peaks and an average heightbetween the valleys and peaks of about 1-2500 nm. The protective coatingcan be substantially transparent.

In accordance with the above objects and those that will be mentionedand will become apparent below, another aspect of the present inventionis a method of forming a protective coating on a receptive surfacecomprising application of a treatment composition comprising: (A) aplurality of hydrophobically modified fumed silica particles obtained bya process comprising the steps of: (a) providing a pre-dispersion ofsilica particles comprising hydrophobically modified fumed silicaparticles by stirring said silica particles into a solution comprising:(i) at least one compound of general formula (I) or (II):

(R¹R²R³Si)₂NR⁴  (I)

-(R¹R²SiNR⁴)_(m)-(cyclo)  (II)

wherein R¹, R² and R³ can be the same or different, and areindependently selected from hydrogen, straight or branched, saturated orunsaturated alkyl chain groups of from 1 to 8 carbon atoms, or aromaticgroups of from 6 to 12 carbon atoms, R⁴ is hydrogen or a methyl group,and m is from 3 to 8; and (ii) a first volatile solvent or solventmixture selected from straight or branched, linear or cyclic aliphatic,or aromatic hydrocarbons with 2 to 14 carbon atoms, monovalent linear orbranched alcohols with 1 to 6 carbon atoms, ketones or aldehydes with 1to 6 carbon atoms, ethers or esters with 2 to 8 carbon atoms, or linearor cyclic polydimethylsiloxanes with 2 to 10 dimethylsiloxy units,wherein the concentration of the hydrophobically modified fumed silicaparticles in the pre-dispersion results in from 10 percent to about 30percent by weight of the total weight of the pre-dispersion, and whereinthe concentration of any one of compounds (I) and/or (II) is between 0.1and 10 percent by weight of the total weight of the pre-dispersion; and(b) mixing with a disperser said pre-dispersion to provide a processcomposition while reducing said silica particles to a median particlesize in the range between 100 and 4000 nanometers; (B) optionally, asuspending agent; (C) optionally, a functional adjunct; and (D)optionally, a propellant.

In accordance with the above objects and those that will be mentionedand will become apparent below, yet another aspect of the presentinvention is a treatment composition for forming a protective coating ona receptive surface comprising: (a) a plurality of particles, whereinsaid particles comprise hydrophobically modified fumed silica particlesin the form of silica particle agglomerates; and (b) a volatile solvent;(c) optionally, a suspending agent; and (d) optionally, a propellant;wherein said treatment composition when applied to said receptivesurface deposits a detachable and renewable protective coating on saidreceptive surface, wherein said protective coating provides dirt- andwater-repellency to said receptive surface. The protective coatingcomprises a non-smooth coating on the receptive surface at least afterthe treatment composition has been applied to the receptive surface andhas substantially dried or set. The non-smooth coating on the receptivesurface includes valleys and peaks and an average height between thevalleys and peaks of about 1-2500 nm. The coating can be substantiallytransparent and result in a change of less than 3.0 Delta E units to thereceptive surface measured before and after deposition of the coating.

In accordance with the above objects and those that will be mentionedand will become apparent below, yet another aspect of the presentinvention is a treatment composition for forming a protective coating ona receptive surface comprising: (a) a plurality of particles, whereinsaid particles comprise hydrophobically modified fumed silica particleshaving a median size of between 100 and 4,000 nanometers; and (b) avolatile solvent; (c) optionally, a suspending agent; and (d)optionally, a propellant; wherein said treatment composition whenapplied to said receptive surface deposits a detachable and renewableprotective coating on said receptive surface, wherein said protectivecoating provides dirt- and water-repellency to said receptive surface.The protective coating comprises a non-smooth coating on the receptivesurface at least after the treatment composition has been applied to thereceptive surface and has substantially dried or set. The non-smoothcoating on the receptive surface includes valleys and peaks and anaverage height between the valleys and peaks of about 1-2500 nm. Thecoating can be substantially transparent and result in a change of lessthan 3.0 Delta E units to the receptive surface measured before andafter deposition of the coating.

In accordance with the above objects and those that will be mentionedand will become apparent below, yet a further aspect of the presentinvention is a treatment composition for forming a protective coating ona receptive surface comprising a plurality of particles comprising: (1)a colloidal dispersion of hydrophobically modified fumed silicaparticles processed by intensively mixing in the presence of at leastone compound of the general formulas (I) and (II)

(R¹R²R³Si)₂NR⁴  (I)

—(R¹R²SiNR⁴)_(m)-(cyclo)  (II)

wherein R¹, R², and R³ can be the same or different and areindependently hydrogen, straight or branched, saturated or unsaturatedalkyl chain groups of from 1 to 8 carbon atoms, optionally substitutedwith flourine atoms, aromatic groups of from 6 to 12 carbon atoms,optionally substituted with flourine atoms, R⁴ is hydrogen or a methylgroup, m is from 3 to 8; and (2) optionally in the presence of at leastone durability agent selected from the group of alkoxysilanes of thegeneral formula (III)

R⁵ _(a)Si(OR⁶)_(4-a)  (III)

wherein R⁵ is a straight or branched, saturated or unsaturated alkylchain group of from 1 to 16 carbon atoms, optionally substituted withflourine atoms, hydroxyl, amino, mercapto, or epoxy groups, R⁶ is analkyl chain of 1 to 2 carbon atoms, a is 1 or 2; or selected form thegroup of alkyl-modified linear or cyclic polydimethylsiloxanes of thegeneral formulas (IV) and (V)

(CH₃)₃SiO[(CH₃)₂SiO]_(n)[(CH₃)R⁷SiO]_(o)Si(CH₃)₃  (IV)

—[(CH₃)₂SiO]_(p)[(CH₃)R⁷SiO]_(q)-(cyclo)  (V)

wherein R⁷ is an alkyl chain group of from 6 to 24 carbon atoms, n isfrom 1 to 100, o from 1 to 40, p from 0 to 7, q from 1 to 7, providedthat the sum (p+q) is at least 3; and a volatile solvent selected fromthe group of aromatic, branched, cyclic, and/or linear hydrocarbons with2 to 14 carbon atoms, optionally substituted with flourine or chlorineatoms, monovalent linear or branched alcohols with 1 to 6 carbon atoms,ethers or esters with 2 to 8 carbon atoms, linear or cyclicpolydimethylsiloxanes with 2 to 10 dimethylsiloxy units, and mixturesthereof; and optionally, a suspending agent; and optionally, apropellant; wherein said treatment composition when applied to saidreceptive surface deposits a detachable and renewable protective coatingon said receptive surface, wherein said protective coating providesdirt- and water-repellency to said receptive surface. The coating can besubstantially transparent and result in a change of less than 3.0 DeltaE units to the receptive surface measured before and after deposition ofthe coating.

In accordance with the above objects and those that will be mentionedand will become apparent below, yet another aspect of the presentinvention is a treatment system for applying and forming a protectivecoating on a receptive surface comprising: (A) an applicator; and (B) atreatment composition for forming a protective coating on said receptivesurface comprising: (i) a plurality of particles, wherein said particlescomprise hydrophobically modified fumed silica particles in the form ofsilica particle agglomerates; and (ii) a volatile solvent; and (iii)optionally, a suspending agent; (iv) optionally, a propellant; and (C)optionally a drying article; wherein said treatment composition whenapplied to said receptive surface deposits a detachable and renewablecoating on said receptive surface, wherein said protective coatingprovides dirt- and water-repellency to said receptive surface. Theprotective coating comprises a non-smooth coating on the receptivesurface at least after the treatment composition has been applied to thereceptive surface and has substantially dried or set. The non-smoothcoating on the receptive surface includes valleys and peaks and anaverage height between the valleys and peaks of about 1-2500 nm. Thecoating can be substantially transparent and result in a change of lessthan 3.0 Delta E units to the receptive surface measured before andafter deposition of the coating.

In accordance with the above objects and those that will be mentionedand will become apparent below, yet another aspect of the presentinvention is a method of forming a detachable and renewable protectivecoating on a receptive surface comprising the steps of: (a) applying atreatment composition to said receptive surface, said treatmentcomposition comprising a plurality of hydrophobically modified fumedsilica particles colloidally dispersed in a volatile solvent; (b)allowing said volatile solvent to evaporate from said receptive surface;and (c) thereby depositing said protective coating on said receptivesurface, wherein said protective coating provides dirt- andwater-repellency to said receptive surface. The protective coatingcomprises a non-smooth coating on the receptive surface at least afterthe treatment composition has been applied to the receptive surface andhas substantially dried or set. The non-smooth coating on the receptivesurface includes valleys and peaks and an average height between thevalleys and peaks of about 1-2500 nm. The detachable coating can besubstantially transparent and result in a change of less than 250 DeltaHaze units to the receptive surface measured before and after depositionof the coating, as measured by the Chrome Test.

In accordance with the above objects and those that will be mentionedand will become apparent below, yet another aspect of the presentinvention is a protective coating on a receptive surface comprising aplurality of hydrophobically modified fumed silica particles obtained bya process comprising the steps of: (a) providing a pre-dispersion ofsilica particles comprising hydrophobically modified fumed silicaparticles by stirring said silica particles into a solution comprising:(i) at least one compound of general formula (I) or (II)

(R¹R²R³Si)₂NR⁴  (I)

—(R¹R²SiNR⁴)_(m)-(cyclo)  (II)

wherein R¹, R² and R³ can be the same or different, and areindependently selected from hydrogen, straight or branched, saturated orunsaturated alkyl chain groups of from 1 to 8 carbon atoms, or aromaticgroups of from 6 to 12 carbon atoms, R⁴ is hydrogen or a methyl group,and m is from 3 to 8; and (ii) a first volatile solvent or solventmixture selected from straight or branched, linear or cyclic aliphatic,or aromatic hydrocarbons with 2 to 14 carbon atoms, monovalent linear orbranched alcohols with 1 to 6 carbon atoms, ketones or aldehydes with 1to 6 carbon atoms, ethers or esters with 2 to 8 carbon atoms, or linearor cyclic polydimethylsiloxanes with 2 to 10 dimethylsiloxy units,wherein the concentration of the hydrophobically modified fumed silicaparticles in the pre-dispersion results in from 10 percent to about 30percent by weight of the total weight of the pre-dispersion, and whereinthe concentration of any one of compounds (I) and/or (II) is between 0.1and 10 percent by weight of the total weight of the pre-dispersion; and(b) mixing with a disperser said pre-dispersion to provide a processcomposition while reducing said silica particles to a median particlesize in the range between 100 and 4000 nanometers; and (c) optionallyadding a durability agent to said solution at step (a) and/or with step(b), wherein said durability agent is selected from alkoxysilanes ofgeneral formula (III)

R⁵ _(a)Si(OR⁶)_(4-a)  (III)

wherein R⁵ is a straight or branched, saturated or unsaturated alkylchain group of from 1 to 16 carbon atoms, optionally substituted withfluorine atoms, hydroxyl, amino, mercapto, or epoxy groups, R⁶ is analkyl chain of 1 to 2 carbon atoms, and a is 1 or 2; or alkyl-modifiedlinear or cyclic polydimethylsiloxanes of general formulas (IV) or (V)

(CH₃)₃SiO[(CH₃)₂SiO]_(n)[(CH₃)R⁷SiO]_(o)Si(CH₃)₃  (IV)

—[(CH₃)₂SiO]_(p)[(CH₃)R⁷SiO]_(q)-(cyclo)  (V)

wherein R⁷ is an alkyl chain group of from 6 to 24 carbon atoms, n isfrom 1 to 100, o is from 1 to 40, p from 0 to 7, and q is from 1 to 7,provided that the sum (p+q) is at least 3, to the dispersion as obtainedin step (b) or step (c), whereby the concentration of any one of thedurability agents (III) and/or (IV) and/or (V) is between 0.01 and 10percent by weight of the total weight of the process composition;wherein said protective coating is detachable and renewable, whereinsaid protective coating provides dirt- and water-repellency to saidreceptive surface. The detachable coating can be substantiallytransparent and result in a change of less than 3.0 Delta E units to thereceptive surface measured before and after deposition of the coating.

In accordance with the above objects and those that will be mentionedand will become apparent below, yet another aspect of the presentinvention is a treated article comprising: (1) a substrate bearing atleast one receptive surface; and (2) a detachable and renewableprotective coating deposited onto said receptive surface, wherein saidprotective coating comprises a plurality of hydrophobically modifiedfumed silica particles obtained by a process comprising the steps of:(a) providing a pre-dispersion of silica particles comprisinghydrophobically modified fumed silica particles by stirring said silicaparticles into a solution comprising: (i) at least one compound ofgeneral formula (I) or (II):

(R¹R²R³Si)₂NR⁴  (I)

—(R¹R²SiNR⁴)_(m)-(cyclo)  (II)

wherein R¹, R² and R³ can be the same or different, and areindependently selected from hydrogen, straight or branched, saturated orunsaturated alkyl chain groups of from 1 to 8 carbon atoms, or aromaticgroups of from 6 to 12 carbon atoms, R⁴ is hydrogen or a methyl group,and m is from 3 to 8; and (ii) a first volatile solvent or solventmixture selected from straight or branched, linear or cyclic aliphatic,or aromatic hydrocarbons with 2 to 14 carbon atoms, monovalent linear orbranched alcohols with 1 to 6 carbon atoms, ketones or aldehydes with 1to 6 carbon atoms, ethers or esters with 2 to 8 carbon atoms, or linearor cyclic polydimethylsiloxanes with 2 to 10 dimethylsiloxy units,wherein the concentration of the hydrophobically modified fumed silicaparticles in the pre-dispersion results in from 10 percent to about 30percent by weight of the total weight of the pre-dispersion, and whereinthe concentration of any one of compounds (I) and/or (II) is between 0.1and 10 percent by weight of the total weight of the pre-dispersion; and(b) mixing with a disperser said pre-dispersion to provide a processcomposition while reducing said silica particles to a median particlesize in the range between 100 and 4000 nanometers; and (c) optionallyadding a durability agent to said solution at step (a) and/or with step(b), wherein said durability agent is selected from alkoxysilanes ofgeneral formula (III)

R⁵ _(a)Si(OR⁶)_(4-a)  (III)

wherein R⁵ is a straight or branched, saturated or unsaturated alkylchain group of from 1 to 16 carbon atoms, optionally substituted withfluorine atoms, hydroxyl, amino, mercapto, or epoxy groups, R⁶ is analkyl chain of 1 to 2 carbon atoms, and a is 1 or 2; or alkyl-modifiedlinear or cyclic polydimethylsiloxanes of general formulas (IV) or (V)

(CH₃)₃SiO[(CH₃)₂SiO]_(n)[(CH₃)R⁷SiO]_(o)Si(CH₃)₃  (IV)

—[(CH₃)₂SiO]_(p)[(CH₃)R⁷SiO]_(q)-(cyclo)  (V)

wherein R⁷ is an alkyl chain group of from 6 to 24 carbon atoms, n isfrom 1 to 100, o is from 1 to 40, p from 0 to 7, and q is from 1 to 7,provided that the sum (p+q) is at least 3, to the dispersion as obtainedin step (b) or step (c), whereby the concentration of any one of thedurability agents (III) and/or (IV) and/or (V) is between 0.01 and 10percent by weight of the total weight of the process composition; andwherein said protective coating provides dirt- and water-repellency tosaid receptive surface. The detachable coating can be substantiallytransparent and result in a change of less than 3.0 Delta E units to thereceptive surface measured before and after deposition of the coating.

Further features and advantages of the present invention will becomeapparent to those of ordinary skill in the art in view of the detaileddescription of preferred embodiments below, when considered togetherwith the attached drawings and claims.

BRIEF DESCRIPTION OF THE DRAWINGS

The foregoing aspects and others will be readily appreciated by theskilled artisan from the following description of illustrativeembodiments when read in conjunction with the accompanying drawings.

FIG. 1 is a scanning electron micrograph (SEM) image of a conventionalLotus effect coating formulation obtained according to the methodsdescribed in U.S. Pat. Pub. No. 2004/0213904, corresponding tocomparative process example H diluted to 0.75 wt. % as active silicawith Dow Corning DC 245 fluid (Comparative Example 21), and applied toan automotive test panel using a PreVal Sprayer according to the testmethods described herein below.

FIG. 2 is an SEM image of one embodiment of an inventive treatmentcomposition, containing about 0.5 wt. % active silica processedaccording to the methods of the present invention according to inventivetreatment composition Example 15, applied to a black automotive testpanel according to the methods of the present invention as describedherein below.

FIG. 3 is an atomic force microscope (AFM) topographical image of atreated black paint panel bearing a renewable coating applied accordingto the present invention.

FIG. 4 is an AFM topographical image of the untreated black paint panelprior to treatment showing the original, unmodified surface.

FIG. 5 is a plot of the rheological profile of a dispersion with arepresentative embodiment of inventive process compositions R and U,processed with and without hexamethyldisilazane, respectively. G′ and G″refer to the viscous and elastic components of the complex rheologicalresponse curves as measured in units of Pascal (Pa) as a function of theoscillation frequency in Hertz (Hz), measured under the conditionsindicated in the process description for the example compositions.

DETAILED DESCRIPTION

Before describing the present invention in detail, it is to beunderstood that this invention is not limited to particularlyexemplified systems or process parameters that may, of course, vary. Itis also to be understood that the terminology used herein is for thepurpose of describing particular embodiments of the invention only, andis not intended to limit the scope of the invention in any manner.

All publications, patents and patent applications cited herein, whethersupra or infra, are hereby incorporated by reference in their entiretyto the same extent as if each individual publication, patent or patentapplication was specifically and individually indicated to beincorporated by reference.

It must be noted that, as used in this specification and the appendedclaims, the singular forms “a,” “an” and “the” include plural referentsunless the content clearly dictates otherwise. Thus, for example,reference to a “surfactant” includes two or more such surfactants.

Unless defined otherwise, all technical and scientific terms used hereinhave the same meaning as commonly understood by one of ordinary skill inthe art to which the invention pertains. Although a number of methodsand materials similar or equivalent to those described herein can beused in the practice of the present invention, the preferred materialsand methods are described herein.

In the application, effective amounts are generally those amounts listedas the ranges or levels of ingredients in the descriptions, which followhereto. Unless otherwise stated, amounts listed in percentage (“%'s”)are in weight percent as indicated as “wt. %”, (based on 100 wt. %active) of the total composition or formulation described.

As used herein, the term “particle” is intended to include any discreteparticle, primary particle, aggregate and/or aggregated collection ofprimary particles, agglomerate and/or agglomerated collection ofaggregates, and/or colloidally dispersed particles, aggregates,agglomerates and/or loose assemblies of particulate materials, andcombinations thereof.

It is noted that particle size determination provides an average ofparticle sizes, generally calculated as a median particle size, of aselected distribution obtained by measuring a sample of material eitherin the form of an aliquot of a liquid composition, and/or a sample ofmaterial in-situ as present as an applied surface coating on a surface.Measurement techniques to determine the particle size differ on thenature of the material, providing for some variability in measuredparticle size distributions, mean, median and average particle sizeparameters, and the like. Measured particle sizes thus typicallyindicate an average value and distribution of all the variousparticulate structures present in the measured system, providing anaverage particle size whose value reflects some proportionalcontribution from all primary, aggregated and/or agglomeratedparticulate structures present.

The median particle size (mass median particle diameter), also referredto as “D50”, is the particle diameter that divides the frequencydistribution in half; fifty percent of the mass has particles with alarger diameter, and fifty percent of the mass has particles with asmaller diameter. According to this definition, the median particlessize as such does not specify whether the particle size distributioncurve is monomodal, bimodal or multimodal. The median particle size isgenerally determinable from a graphic plot of the cumulative integratedarea under the curve obtained from a particle size histogram analysis ofthe respective system measured.

“Specific surface area” means the surface area per unit weight of aparticulate solid, e.g. as determined by the B.E.T. (Brunauer, Emmett,and Teller) method.

As stated above, one aspect of the invention is a method of forming adetachable and renewable protective coating on a receptive surfacecomprising the steps of: (a) applying a treatment composition to saidreceptive surface, said treatment composition comprising a plurality ofhydrophobically modified fumed silica particles colloidally dispersed ina volatile solvent; (b) allowing said volatile solvent to evaporate fromsaid receptive surface; and (c) thereby depositing said protectivecoating on said receptive surface, wherein said protective coatingprovides dirt- and water-repellency to said receptive surface. Theprotective coating comprises a non-smooth coating on the receptivesurface at least after the treatment composition has been applied to thereceptive surface and has substantially dried or set. The non-smoothcoating on the receptive surface includes valleys and peaks and anaverage height between the valleys and peaks of about 1-2500 nm. Thedetachable coating can be substantially transparent and result in achange of less than 3.0 Delta E units to the receptive surface measuredbefore and after deposition of the coating.

In one embodiment, the method employs a treatment composition comprising(A) a plurality of hydrophobically modified fumed silica particlesobtained by a process comprising the steps of: (a) providing apre-dispersion of silica particles comprising hydrophobically modifiedfumed silica particles by stirring said silica particles into a solutioncomprising: (i) at least one compound of general formula (I) or (II):

(R¹R²R³Si)₂NR⁴  (I)

—(R¹R²SiNR⁴)_(m)-(cyclo)  (II)

wherein R¹, R² and R³ can be the same or different, and areindependently selected from hydrogen, straight or branched, saturated orunsaturated alkyl chain groups of from 1 to 8 carbon atoms, or aromaticgroups of from 6 to 12 carbon atoms, R⁴ is hydrogen or a methyl group,and m is from 3 to 8, and (ii) a first volatile solvent or solventmixture selected from straight or branched, linear or cyclic aliphatic,or aromatic hydrocarbons with 2 to 14 carbon atoms, monovalent linear orbranched alcohols with 1 to 6 carbon atoms, ketones or aldehydes with 1to 6 carbon atoms, ethers or esters with 2 to 8 carbon atoms, or linearor cyclic polydimethylsiloxanes with 2 to 10 dimethylsiloxy units,wherein the concentration of the hydrophobically modified fumed silicaparticles in the pre-dispersion results in from 10 percent to about 30percent by weight of the total weight of the pre-dispersion, and whereinthe concentration of any one of compounds (I) and/or (II) is between 0.1and 10 percent by weight of the total weight of the pre-dispersion; andthen (b) mixing with a disperser said pre-dispersion to provide aprocess composition while reducing said silica particles to a medianparticle size in the range between 100 and 4000 nanometers, and furtherincluding (B) an optional suspending agent, (C) an optional functionaladjunct and (D) an optional propellant.

In yet another embodiment, the process solution used to obtain theinventive treatment compositions of the present invention furthercomprises at least one durability agent selected from alkoxysilanes ofgeneral formula (III)

R⁵ _(a)Si(OR⁶)_(4-a)  (III)

wherein R⁵ is a straight or branched, saturated or unsaturated alkylchain group of from 1 to 16 carbon atoms, optionally substituted withfluorine atoms, hydroxyl, amino, mercapto, or epoxy groups, R⁶ is analkyl chain of 1 to 2 carbon atoms, and a is 1 or 2; or alkyl-modifiedlinear or cyclic polydimethylsiloxanes of general formula (IV) or (V)

(CH₃)₃SiO[(CH₃)₂SiO]_(n)[(CH₃)R⁷SiO]_(o)Si(CH₃)₃  (IV)

-[(CH₃)₂SiO]_(p)[(CH₃)R⁷SiO]_(q)-(cyclo)  (V)

wherein R⁷ is an alkyl chain group of from 6 to 24 carbon atoms, n isfrom 1 to 100, o is from 1 to 40, p from 0 to 7, and q is from 1 to 7,provided that the sum (p+q) is at least 3; whereby the concentration ofany one of the durability agents (III) and/or (IV) and/or (V) is between0.1 and 10 percent by weight of the total weight of the pre-dispersion.

In an alternative embodiment, the method can further comprise (c)diluting the process composition with a second volatile solvent orsolvent mixture selected from straight or branched, linear or cyclicaliphatic, or aromatic hydrocarbons with 2 to 14 carbon atoms,optionally substituted with fluorine or chlorine atoms, monovalentlinear or branched alcohols with 1 to 6 carbon atoms, ketones oraldehydes with 1 to 6 carbon atoms, ethers or esters with 2 to 8 carbonatoms, or linear or cyclic polydimethylsiloxanes with 2 to 10dimethylsiloxy units to a final concentration of the hydrophobicallymodified fumed silica particles of minimum 5 percent by weight of thetotal weight of the process composition.

In another alternative embodiment, the method can further be augmentedby adding a durability agent to the process composition wherein saiddurability agent is selected from alkoxysilanes of general formula (III)

R⁵ _(a)Si(OR⁶)_(4-a)  (III)

wherein R⁵ is a straight or branched, saturated or unsaturated alkylchain group of from 1 to 16 carbon atoms, optionally substituted withfluorine atoms, hydroxyl, amino, mercapto, or epoxy groups, R⁶ is analkyl chain of 1 to 2 carbon atoms, and a is 1 or 2; or alkyl-modifiedlinear or cyclic polydimethylsiloxanes of general formulas (IV) or (V)

(CH₃)₃SiO[(CH₃)₂SiO]_(n)[(CH₃)R⁷SiO]_(o)Si(CH₃)₃  (IV)

—[(CH₃)₂SiO]_(p)[(CH₃)R⁷SiO]_(q)-(cyclo)  (V)

wherein R⁷ is an alkyl chain group of from 6 to 24 carbon atoms, n isfrom 1 to 100, o is from 1 to 40, p from 0 to 7, and q is from 1 to 7,provided that the sum (p+q) is at least 3, to the dispersion as obtainedin step (b) or step (c), whereby the concentration of any one of thedurability agents (III) and/or (IV) and/or (V) is between 0.01 and 10percent by weight of the total weight of the process composition.

In yet another embodiment of the present invention, the hydrophobicallymodified fumed silica particles have a median particle size of between100 and 4,000 nanometers, and alternatively have a median particle sizeof between 100 and 3,000 nanometers, and yet alternatively have a medianparticle size of between 100 and 1,000 nanometers.

In one embodiment of the present invention, the method of forming adetachable and renewable protective coating on a receptive surfacecomprises forming the coating onto a receptive surface selected from anon-porous substrate, porous substrate, and combinations thereof.Suitable receptive surfaces include, but are not limited to those foundon automotive surfaces, household interior surfaces, household exteriorsurfaces, articles of construction, and combinations thereof.

In another embodiment of the present invention, the method of forming adetachable protective coating on a non-porous substrate produces acoating that is substantially transparent and results in a change ofless than 3.0 Delta E units of said non-porous substrate afterapplication of said detachable coating.

In another embodiment of the present invention, the method of forming adetachable protective coating on a non-porous substrate produces acoating that is substantially not transparent and results in a change ofmore than 3.0 Delta E units of said non-porous substrate afterapplication of said detachable coating.

In yet another embodiment of the present invention, the method offorming a detachable protective coating on a porous surface produces acoating that is substantially transparent and results in a change ofless than 3.0 Delta L units of said porous substrate after applicationof said detachable coating.

In yet another embodiment of the present invention, the method offorming a detachable protective coating on a porous surface produces acoating that is substantially not transparent and results in a change ofmore than 3.0 Delta L units of said porous substrate after applicationof said detachable coating.

In yet a further embodiment of the present invention, the method offorming a detachable protective coating employing the inventivetreatment compositions produces a detachable and renewable protectivecoating comprising hydrophobically modified fumed silica particlesdeposited onto a treated surface or treated article wherein the coatingis sufficiently durable to exhibit a Durability Duration value ofgreater than or equal to 15 seconds.

In another embodiment of the present invention is a treatmentcomposition for forming a detachable and renewable protective coating ona receptive surface comprising: (a) 0.05 to 5.0 percent by weight of aplurality of hydrophobically modified fumed silica particles having amedian particle size of between 100 and 4,000 nanometers; (b) 99.95 to 5percent by weight of a volatile solvent; (c) optionally, 0.001 to 5percent by weight of a suspending agent; (d) optionally, 0.001 to 5percent by weight of a functional adjunct; and optionally, in balance to100 percent by weight if present, a propellant, which provides atreatment composition that when applied to said receptive surfacedeposits said protective coating on said receptive surface, wherein saidprotective coating provides dirt- and water-repellency to said receptivesurface. The protective coating comprises a non-smooth coating on thereceptive surface at least after the treatment composition has beenapplied to the receptive surface and has substantially dried or set. Thenon-smooth coating on the receptive surface includes valleys and peaksand an average height between the valleys and peaks of about 1-2500 nm.The detachable coating can be substantially transparent and result in achange of less than 3.0 Delta E units to the receptive surface measuredbefore and after deposition of the coating.

In another embodiment of the invention, the treatment compositionsemployed for producing the detachable and renewable protective coatingsof the present invention are obtained by dilution of a processcomposition comprising a plurality of hydrophobically modified fumedsilica particles obtained by a process comprising the steps of: (a)providing a pre-dispersion of silica particles comprisinghydrophobically modified fumed silica particles by stirring said silicaparticles into a solution comprising: (i) at least one compound ofgeneral formula (I) or (II):

(R¹R²R³Si)₂NR⁴  (I)

—(R¹R²SiNR⁴)_(m)-(cyclo)  (II)

wherein R¹, R² and R³ can be the same or different, and areindependently selected from hydrogen, straight or branched, saturated orunsaturated alkyl chain groups of from 1 to 8 carbon atoms, or aromaticgroups of from 6 to 12 carbon atoms, R⁴ is hydrogen or a methyl group,and m is from 3 to 8; and (ii) a first volatile solvent or solventmixture selected from straight or branched, linear or cyclic aliphatic,or aromatic hydrocarbons with 2 to 14 carbon atoms, monovalent linear orbranched alcohols with 1 to 6 carbon atoms, ketones or aldehydes with 1to 6 carbon atoms, ethers or esters with 2 to 8 carbon atoms, or linearor cyclic polydimethylsiloxanes with 2 to 10 dimethylsiloxy units,wherein the concentration of the hydrophobically modified fumed silicaparticles in the pre-dispersion results in from 10 percent to about 30percent by weight of the total weight of the pre-dispersion, and whereinthe concentration of any one of compounds (I) and/or (II) is between 0.1and 10 percent by weight of the total weight of the pre-dispersion; andthen (b) mixing with a disperser said pre-dispersion to provide aprocess composition while reducing said silica particles to a medianparticle size in the range between 100 and 4000 nanometers; and further(c) optionally adding a durability agent to said solution at step (a)and/or with step (b), wherein said durability agent is selected fromalkoxysilanes of general formula (III)

R⁵ _(a)Si(OR⁶)_(4-a)  (III)

wherein R⁵ is a straight or branched, saturated or unsaturated alkylchain group of from 1 to 16 carbon atoms, optionally substituted withfluorine atoms, hydroxyl, amino, mercapto, or epoxy groups, R⁶ is analkyl chain of 1 to 2 carbon atoms, and a is 1 or 2; or alkyl-modifiedlinear or cyclic polydimethylsiloxanes of general formulas (IV) or (V)

(CH₃)₃SiO[(CH₃)₂SiO]_(n)[(CH₃)R⁷SiO]_(o)Si(CH₃)₃  (IV)

-[(CH₃)₂SiO]_(p)[(CH₃)R⁷SiO]_(q)-(cyclo)  (V)

wherein R⁷ is an alkyl chain group of from 6 to 24 carbon atoms, n isfrom 1 to 100, o is from 1 to 40, p from 0 to 7, and q is from 1 to 7,provided that the sum (p+q) is at least 3, to the dispersion as obtainedin step (b) or step (c), whereby the concentration of any one of thedurability agents (III) and/or (IV) and/or (V) is between 0.01 and 10percent by weight of the total weight of the process composition.

In another embodiment of the present invention, treatment compositionscontain a volatile solvent that is selected from the group of aromatic,branched, cyclic, and/or linear hydrocarbons with 2 to 14 carbon atoms,optionally substituted with fluorine or chlorine atoms, monovalentlinear or branched alcohols with 1 to 6 carbon atoms, aldehydes andketones, ethers or esters with 2 to 8 carbon atoms, linear or cyclicpolydimethylsiloxanes with 2 to 10 dimethylsiloxy units, and mixturesthereof.

In yet a further embodiment of the present invention, treatmentcompositions contain a suspending agent selected from the groupconsisting of polymers, surfactants, and mixtures thereof in order toprovide improved or extended storage stability or stability underadverse conditions.

In still another embodiment of the present invention, treatmentcompositions further incorporate a functional adjunct to exhibit afurther benefit, wherein said functional adjunct is selected from thegroup consisting of ultraviolet light absorbers, ultraviolet lightblockers, free-radical scavengers, fluorescent whitening agents,colorants, dyes, pigments, photoactive particles, color changing dyes,color fading dyes, bleaching agents, fixative agents, spreading agents,evaporation modifiers, azeotropic cosolvents, stabilizers, perfume,fragrance, odor control agents, anti-static agents, thickeners, andmixtures thereof.

In a further embodiment of the present invention, a treatment system orkit can be employed for applying and forming a detachable and renewableprotective coating on a receptive surface, wherein the treatment systemor kit comprises: (a) an applicator; and (b) a treatment composition forforming a protective coating on said receptive surface comprising: (i)0.05 to 5.0 percent by weight of a plurality of hydrophobically modifiedfumed silica particles having a median particle size of between 100 and4,000 nanometers; (ii) 99.95 to 5 percent by weight of a volatilesolvent; (iii) optionally, 0.001 to 5 percent by weight of a suspendingagent; (iv) optionally, (v) 0.001 to 5 percent by weight of a functionaladjunct; and (vi) optionally, in balance to 100 percent by weight ifpresent, a propellant; and further (c) optionally, a drying article;wherein said treatment composition when applied to said receptivesurface deposits said protective coating on said receptive surface,wherein said protective coating provides dirt- and water-repellency tosaid receptive surface, wherein said receptive surface is a non-poroussubstrate and/or a porous substrate. The protective coating comprises anon-smooth coating on the receptive surface at least after the treatmentcomposition has been applied to the receptive surface and hassubstantially dried or set. The non-smooth coating on the receptivesurface includes valleys and peaks and an average height between thevalleys and peaks of about 1-2500 nm. The detachable coating can besubstantially transparent and results in a change of less than 3.0 DeltaE units to the non-porous substrate and/or results in a change of lessthan 3.0 Delta L units to said porous substrate, measured before andafter deposition of the coating.

In an alternative embodiment of the present invention relating to thatembodiment presented immediately above, the treatment system employs anapplicator comprising a device capable of dispensing said treatmentcomposition in the form of a fine spray comprising a plurality of liquiddroplets, and capable of directing said plurality of liquid dropletsonto said receptive surface.

In yet another embodiment of the present invention, the treatment systememploys an applicator comprising a pressurized aerosol container inwhich the treatment composition according to the present invention ischarged.

In an additional embodiment of the present invention, the treatmentsystem employs an applicator comprising a non-pressurized delivery meansfor dispensing and applying the inventive treatment compositions onto areceptive surface.

In yet a further embodiment of the present invention is a method offorming a detachable and renewable protective coating on a receptivesurface comprising the steps of: (a) applying a treatment composition tosaid receptive surface, said treatment composition comprising aplurality of hydrophobically modified fumed silica particles colloidallydispersed in a volatile solvent; (b) allowing said volatile solvent toevaporate from said receptive surface; and (c) thereby depositing saidprotective coating on said receptive surface, wherein said protectivecoating provides dirt- and water-repellency to said receptive surface.wherein said detachable coating is substantially transparent and resultsin a change of less than 250 Delta Haze units to said receptive surfacemeasured before and after deposition of said coating, as measured by theChrome Test.

In another embodiment of the present invention, a treatment compositionis employed for forming a detachable and renewable protective coating ona receptive surface, wherein said treatment composition comprises: (a)0.05 to 5.0 percent by weight of a plurality of hydrophobically modifiedfumed silica particles having a median particle size of between 100 and4,000 nanometers; (b) 99.95 to 5 percent by weight of a volatilesolvent; (c) optionally, 0.001 to 5 percent by weight of a suspendingagent; (d) optionally, 0.001 to 5 percent by weight of a functionaladjunct; and (e) optionally, in balance to 100 percent by weight ifpresent, a propellant; wherein said treatment composition when appliedto said receptive surface deposits said protective coating on saidreceptive surface, wherein said protective coating provides dirt- andwater-repellency to said receptive surface, and wherein said coating issubstantially transparent and results in a change of less than 250 DeltaHaze units to said receptive surface measured before and afterdeposition of said coating, as measured by the Chrome Test.

In yet one further embodiment of the present invention, a treatmentcomposition is employed for forming a detachable and renewableprotective coating on a receptive surface, wherein said hydrophobicallymodified fumed silica particles have a median particle size of less than2,000 nanometers and wherein said coating resulting from use of theinventive treatment composition results in a coating exhibiting a changeof less than 200 Delta Haze units on said surface, and alternativelywherein said hydrophobically modified fumed silica particles have amedian particle size of less than 1,000 nanometers and wherein saidcoating resulting from use of the inventive treatment compositionresults in a coating exhibiting a change of less than 100 Delta Hazeunits on said surface.

In another embodiment of the present invention, use of the inventivetreatment compositions provides a treated article comprising: (1) asubstrate bearing at least one receptive surface; and (2) a detachableand renewable protective coating deposited onto said receptive surface,wherein said protective coating comprises a plurality of hydrophobicallymodified fumed silica particles obtained by a process comprising thesteps of: (a) providing a pre-dispersion of silica particles comprisinghydrophobically modified fumed silica particles by stirring said silicaparticles into a solution comprising: (i) at least one compound ofgeneral formula (I) or (II):

(R¹R²R³Si)₂NR⁴  (I)

—(R¹R²SiNR⁴)_(m)-(cyclo)  (II)

wherein R¹, R² and R³ can be the same or different, and areindependently selected from hydrogen, straight or branched, saturated orunsaturated alkyl chain groups of from 1 to 8 carbon atoms, or aromaticgroups of from 6 to 12 carbon atoms, R⁴ is hydrogen or a methyl group,and m is from 3 to 8; and (ii) a first volatile solvent or solventmixture selected from straight or branched, linear or cyclic aliphatic,or aromatic hydrocarbons with 2 to 14 carbon atoms, monovalent linear orbranched alcohols with 1 to 6 carbon atoms, ketones or aldehydes with 1to 6 carbon atoms, ethers or esters with 2 to 8 carbon atoms, or linearor cyclic polydimethylsiloxanes with 2 to 10 dimethylsiloxy units,wherein the concentration of the hydrophobically modified fumed silicaparticles in the pre-dispersion results in from 10 percent to about 30percent by weight of the total weight of the pre-dispersion, and whereinthe concentration of any one of compounds (I) and/or (II) is between 0.1and 10 percent by weight of the total weight of the pre-dispersion; and(b) mixing with a disperser said pre-dispersion to provide a processcomposition while reducing said silica particles to a median particlesize in the range between 100 and 4000 nanometers; and (c) optionallyadding a durability agent to said solution at step (a) and/or with step(b), wherein said durability agent is selected from alkoxysilanes ofgeneral formula (III)

R⁵ _(a)Si(OR⁶)_(4-a)  (III)

wherein R⁵ is a straight or branched, saturated or unsaturated alkylchain group of from 1 to 16 carbon atoms, optionally substituted withfluorine atoms, hydroxyl, amino, mercapto, or epoxy groups, R⁶ is analkyl chain of 1 to 2 carbon atoms, and a is 1 or 2; or alkyl-modifiedlinear or cyclic polydimethylsiloxanes of general formulas (IV) or (V)

(CH₃)₃SiO[(CH₃)₂SiO]_(n)[(CH₃)R⁷SiO]_(o)Si(CH₃)₃  (IV)

—[(CH₃)₂SiO]_(p)[(CH₃)R⁷SiO]_(q)-(cyclo)  (V)

wherein R⁷ is an alkyl chain group of from 6 to 24 carbon atoms, n isfrom 1 to 100, o is from 1 to 40, p from 0 to 7, and q is from 1 to 7,provided that the sum (p+q) is at least 3, to the dispersion as obtainedin step (b) or step (c), whereby the concentration of any one of thedurability agents (III) and/or (IV) and/or (V) is between 0.01 and 10percent by weight of the total weight of the process composition; andwherein said protective coating provides dirt- and water-repellency tosaid receptive surface, wherein said detachable coating is substantiallytransparent and results in a change of less than 3.0 Delta E units tosaid receptive surface measured before and after deposition of saidcoating.

In another embodiment of the present invention, the treated articleresults when said protective coating is formed by use of a treatmentcomposition comprising: (a) 0.05 to 5.0 percent by weight of a pluralityof hydrophobically modified fumed silica particles having a medianparticle size of between 100 and 4,000 nanometers; (b) 99.95 to 5percent by weight of a volatile solvent; (c) optionally, 0.001 to 5percent by weight of a suspending agent; (d) optionally, 0.001 to 5percent by weight of a functional adjunct; and (e) optionally, inbalance to 100 percent by weight if present, a propellant.

In yet a further embodiment of the present invention, a protectivecoating on a receptive surface comprises a plurality of hydrophobicallymodified fumed silica particles obtained by a process comprising thesteps of: (a) providing a pre-dispersion of silica particles comprisinghydrophobically modified fumed silica particles by stirring said silicaparticles into a solution comprising: (i) at least one compound ofgeneral formula (I) or (II)

(R¹R²R³Si)₂NR⁴  (I)

—(R¹R²SiNR⁴)_(m)-(cyclo)  (II)

wherein R¹, R² and R³ can be the same or different, and areindependently selected from hydrogen, straight or branched, saturated orunsaturated alkyl chain groups of from 1 to 8 carbon atoms, or aromaticgroups of from 6 to 12 carbon atoms, R⁴ is hydrogen or a methyl group,and m is from 3 to 8; and (ii) a first volatile solvent or solventmixture selected from straight or branched, linear or cyclic aliphatic,or aromatic hydrocarbons with 2 to 14 carbon atoms, monovalent linear orbranched alcohols with 1 to 6 carbon atoms, ketones or aldehydes with 1to 6 carbon atoms, ethers or esters with 2 to 8 carbon atoms, or linearor cyclic polydimethylsiloxanes with 2 to 10 dimethylsiloxy units,wherein the concentration of the hydrophobically modified fumed silicaparticles in the pre-dispersion results in from 10 percent to about 30percent by weight of the total weight of the pre-dispersion, and whereinthe concentration of any one of compounds (I) and/or (II) is between 0.1and 10 percent by weight of the total weight of the pre-dispersion; and(b) mixing with a disperser said pre-dispersion to provide a processcomposition while reducing said silica particles to a median particlesize in the range between 100 and 4000 nanometers; and then (c)optionally adding a durability agent to said solution at step (a) and/orwith step (b), wherein said durability agent is selected fromalkoxysilanes of general formula (III)

R⁵ _(a)Si(OR⁶)_(4-a)  (III)

wherein R⁵ is a straight or branched, saturated or unsaturated alkylchain group of from 1 to 16 carbon atoms, optionally substituted withfluorine atoms, hydroxyl, amino, mercapto, or epoxy groups, R⁶ is analkyl chain of 1 to 2 carbon atoms, and a is 1 or 2; or alkyl-modifiedlinear or cyclic polydimethylsiloxanes of general formulas (IV) or (V)

(CH₃)₃SiO[(CH₃)₂SiO]_(n)[(CH₃)R⁷SiO]_(o)Si(CH₃)₃  (IV)

[(CH₃)₂SiO]_(p)[(CH₃)R⁷SiO]_(q)-(cyclo)  (V)

wherein R⁷ is an alkyl chain group of from 6 to 24 carbon atoms, n isfrom 1 to 100, o is from 1 to 40, p from 0 to 7, and q is from 1 to 7,provided that the sum (p+q) is at least 3, to the dispersion as obtainedin step (b) or step (c), whereby the concentration of any one of thedurability agents (III) and/or (IV) and/or (V) is between 0.01 and 10percent by weight of the total weight of the process composition;wherein said protective coating is detachable and renewable, whereinsaid protective coating provides dirt- and water-repellency to saidreceptive surface, and wherein said detachable coating is substantiallytransparent and results in a change of less than 3.0 Delta E units tosaid receptive surface measured before and after deposition of saidcoating.

Treatment Composition

Methods and treatment systems according to the present invention employtreatment compositions comprising a plurality of particles comprising acolloidal dispersion of hydrophobically modified fumed silica particles,a volatile solvent, optionally processed in the presence of or furthercomprising a durability agent, and other optional additives including asuspending agent, functional adjunct, and propellant.

In an embodiment, the treatment composition is formulated to form anon-smooth coating on a receptive surface at least after the compositionhas been applied to the receptive surface and has substantially dried orset. The treatment composition can include a first and second set ofhydrophobically modified fumed silica colloidal particles. Each of thefirst and second sets of hydrophobically modified fumed silica colloidalparticles includes a plurality of colloidal particles. The first set ofhydrophobically modified fumed silica colloidal particles can have anaverage particle size that is greater than the average size of thesecond set of hydrophobically modified fumed silica colloidal particles.The number of hydrophobically modified fumed silica colloidal particlesin the second set of colloidal particles can be greater than the numberof hydrophobically modified fumed silica colloidal particles in thefirst set of colloidal particles. One or more of the hydrophobicallymodified fumed silica colloidal particles can be modified to include oneor more hydrocarbon chains.

The inclusion of at least two colloidal particles having a differentsize is believed to form elevations and depressions on a material uponwhich these particles have been deposited. As can be appreciated, thesecolloidal particles can be applied to different types of materials by avariety of mechanisms. For instance, when the colloidal particles areapplied to hard surfaces (e.g., glass surfaces, tile surfaces, granitesurfaces, formica surfaces, linoleum surfaces, concrete or concretecomposite surfaces, metal surfaces, wood surfaces, ceramic surfaces,etc.), the colloidal particles can be applied by a solid solution (e.g.,wax, paste, etc.), a liquid solution, and/or by an aerosol. When it isdesired to apply the colloidal particles to a non-hard surface (e.g.,fabric surfaces, leather surfaces, carpet, woven or non-woven materials,etc.); the solid colloidal particles can be applied by a solid solution,a liquid solution, and/or by an aerosol.

The colloidal particle containing composition of the present inventioncontains at least two different sized colloidal particles. It isbelieved that the differing sized colloidal particles, when applied to asurface, result in the colloidal particles stacking on top of oneanother to form non-smooth surfaces. These non-smooth surfaces arebelieved to be at least partially caused by the non-uniform particlesizes of the colloidal particles. The non-smooth surfaces generally havean average height between the valleys and peaks of the non-smoothsurfaces of up to about 2500 nm; however, it can be appreciated thatlarger average heights can be achieved. In one non-limiting example, theaverage height between the valleys and peaks of the non-smooth surfacesis about 1-2000 nm. In another non-limiting example, the average heightbetween the valleys and peaks of the non-smooth surfaces is about 1-1500nm. In another non-limiting example, the average height between thevalleys and peaks of the non-smooth surfaces is about 1-1000 nm. Inanother non-limiting example, the average height between the valleys andpeaks of the non-smooth surfaces is about 1-500 nm. In still anothernon-limiting example, the average height between the valleys and peaksof the non-smooth surfaces is about 5-250 nm. In yet anothernon-limiting example, the average height between the valleys and peaksof the non-smooth surfaces is 10-100 nm. In still yet anothernon-limiting example, the average height between the valleys and peaksof the non-smooth surfaces is 20-80 nm.

These small elevations and depressions on the surface of a material canat least partially result in a lotus effect on the surface of thematerial. As such, liquids (e.g., water, etc.) that contact a surfacethat includes these small elevations and depressions have a tendency torunoff such surfaces, thereby reducing the opportunity of such liquidsto be absorbed into such surfaces and/or dry on and stain such surfaces.

The particle size ratio of at least two sized sets of colloidalparticles in the colloidal particle containing composition of thepresent invention is at least about 1.02:1. In one non-limiting aspectof this embodiment, the average size ratio of at least two differentsized colloidal particles is at least about 1.05:1. In anothernon-limiting aspect of this embodiment, the average size ratio of atleast two different sized colloidal particles is at least about 1.1:1.In another non-limiting aspect of this embodiment, the average sizeratio of at least two different sized colloidal particles is at leastabout 1.5:1. In still another non-limiting aspect of this embodiment,the average size ratio of at least two different sized colloidalparticles is at least about 2:1. In yet another non-limiting aspect ofthis embodiment, the average size ratio of at least two different sizedcolloidal particles is about 2-20:1. In still yet another non-limitingaspect of this embodiment, the average size ratio of at least twodifferent sized colloidal particles is about 2-10:1. In still yetanother non-limiting aspect of this embodiment, the average size ratioof at least two different sized colloidal particles is about 2.5-8:1. Inanother non-limiting aspect of this embodiment, the average size ratioof at least two different sized colloidal particles is about 3-7:1. Instill another non-limiting aspect of this embodiment, the average sizeratio of at least two different sized colloidal particles is about5-7:1. In yet another non-limiting aspect of this embodiment, theaverage size ratio of at least two different sized colloidal particlesis about 3-5:1. As can be appreciated, other size ratios can be used. Inanother and/or alternative one non-limiting embodiment of the invention,the number of colloidal particles that are included in each set of sizedcolloidal particles is controlled to obtain the desired non-smoothsurfaces on the surface of a material that is coated with the colloidalparticle containing composition of the present invention.

Generally, the number of small colloidal particles in the colloidalparticle containing composition of the present invention is greater thanthe number of larger colloidal particles. In one non-limiting aspect ofthis embodiment, the ratio of the number of small colloidal particles ofat least one set of colloidal particles having some average size to thenumber of larger colloidal particles in at least one other set ofcolloidal particles having some average size is at least about 1.5:1. Inyet another non-limiting aspect of this embodiment, the ratio of thenumber of small colloidal particles of at least one set of colloidalparticles having some average size to the number of larger colloidalparticles in at least one other set of colloidal particles having someaverage size is at least about 2:1. In still another non-limiting aspectof this embodiment, the ratio of the number of small colloidal particlesof at least one set of colloidal particles having some average size tothe number of larger colloidal particles in at least one other set ofcolloidal particles having some average size is at least about 5:1. Instill another non-limiting aspect of this embodiment, the ratio of thenumber of small colloidal particles of at least one set of colloidalparticles having some average size to the number of larger colloidalparticles in at least one other set of colloidal particles having someaverage size is at least about 10:1. In yet another non-limiting aspectof this embodiment, the ratio of the number of small colloidal particlesof at least one set of colloidal particles having some average size tothe number of larger colloidal particles in at least one other set ofcolloidal particles having some average size is at least about 20:1. Instill yet another non-limiting aspect of this embodiment, the ratio ofthe number of small colloidal particles of at least one set of colloidalparticles having some average size to the number of larger colloidalparticles in at least one other set of colloidal particles having someaverage size is about 10-1000:1. In another non-limiting aspect of thisembodiment, the ratio of the number of small colloidal particles of atleast one set of colloidal particles having some average size to thenumber of larger colloidal particles in at least one other set ofcolloidal particles having some average size is about 15-500:1. In stillanother non-limiting aspect of this embodiment, the ratio of the numberof small colloidal particles of at least one set of colloidal particleshaving some average size to the number of larger colloidal particles inat least one other set of colloidal particles having some average sizeis about 20-300:1. In yet another non-limiting aspect of thisembodiment, the ratio of the number of small colloidal particles of atleast one set of colloidal particles having some average size to thenumber of larger colloidal particles in at least one other set ofcolloidal particles having some average size is about 30-200:1. In stillyet another non-limiting aspect of this embodiment, the ratio of thenumber of small colloidal particles of at least one set of colloidalparticles having some average size to the number of larger colloidalparticles in at least one other set of colloidal particles having someaverage size is about 70-150:1. As can be appreciated, other number ofparticle ratios can be used.

The colloidal particle containing composition of the present inventioncan have a controlled maximum average size of colloidal particles in thecolloidal particle containing composition of the present invention so asto achieve one or more of the desired properties of the colloidalparticle containing composition. For instance, when the colloidalparticle containing composition is to be used on a glass surface and/oris used to form a substantially transparent coating, the maximum size ofthe colloidal particles is generally below 1000 nm, since largerparticle colloidal particles can cause the coating to be cloudy and/orcolored. In other applications wherein clear coatings are not essential,colloidal particles can have a size that is less than, equal to, orgreater than about 1000 nm. In one non-limiting specific example, thecolloidal particle containing composition of the present invention doesnot include colloidal particles that are greater than about 25000 nm.

In another one non-limiting specific example, the colloidal particlecontaining composition of the present invention includes a maximum setsize of colloidal particles that has an average size of less than about5000 nm. In still another one non-limiting specific example, thecolloidal particle containing composition of the present inventionincludes a maximum set size of colloidal particles that has an averagesize of less than about 2000 nm. In yet another one non-limitingspecific example, the colloidal particle containing composition of thepresent invention includes a maximum set size of colloidal particlesthat has an average size of less than about 500 nm.

In still yet another one non-limiting specific example, the colloidalparticle containing composition of the present invention includes oneset of colloidal particles having an average size of about 2-40 nm and asecond set of colloidal particles having an average size of about 15-200nm. In another one non-limiting specific example, the colloidal particlecontaining composition of the present invention includes one set ofcolloidal particles having an average size of about 2-20 nm and a secondset of colloidal particles having an average size of about 15-100 nm. Inyet another non-limiting specific example, the colloidal particlecontaining composition of the present invention contains one set ofcolloidal particles having an average size of about 3-15 nm and a secondset of colloidal particles having an average size of about 16-50 nm. Instill yet another non-limiting specific example, the colloidal particlecontaining composition of the present invention contains one set ofcolloidal particles having an average size of about 4-10 nm and a secondset of colloidal particles having an average size of about 18-40 nm. Ascan be appreciated, other sized particles for the first and/or secondset of particles can be used.

As can also or alternatively be appreciated, more than two sets ofcolloidal particles having different average particle sizes can beincluded in the colloidal particle containing compositions. Forinstance, the colloidal particle containing composition of the presentinvention can include from about 2-10 sized sets of colloidal particleshaving different average particle sizes.

The colloidal particle containing material of the present invention caninclude one or more sets of colloidal particles that have been modified.The colloidal particles can be modified to 1) control the size of thecolloidal particles, 2) improve the bonding between a plurality ofcolloidal particles when applied to a surface, 3) improve the bondingbetween a plurality of colloidal particles and the surface to which thecolloidal particles are applied, 4) increase the packing density betweena plurality of colloidal particles, and/or 5) increase thehydrophobicity of colloidal particles when applied to a surface. As canbe appreciated, one or more colloidal particles can be modified forother or additional reasons.

In an example of an embodiment of the present invention, a treatmentcomposition is obtained by a dilution step employing a second solventadded to a process composition comprising: (a) 5 to 30 percent by weightof hydrophobically modified fumed silica particles with a medianparticle size in the range between 100 and 4000 nanometers; and (b) 50to 95 percent by weight of a first volatile solvent or solvent mixtureselected from straight or branched, linear or cyclic aliphatic, oraromatic hydrocarbons with 2 to 14 carbon atoms, monovalent linear orbranched alcohols with 1 to 6 carbon atoms, ketones or aldehydes with 1to 6 carbon atoms, ethers or esters with 2 to 8 carbon atoms, or linearor cyclic polydimethyl-siloxanes with 2 to 10 dimethylsiloxy units; suchthat the said dilution step results in less than 5 percent by weight ofsaid hydrophobically modified fumed silica particles in said treatmentcomposition; wherein said second solvent comprises a volatile solvent orsolvent mixture selected from straight or branched, linear or cyclicaliphatic, or aromatic hydrocarbons with 2 to 14 carbon atoms,monovalent linear or branched alcohols with 1 to 6 carbon atoms, ketonesor aldehydes with 1 to 6 carbon atoms, ethers or esters with 2 to 8carbon atoms, or linear or cyclic polydimethylsiloxanes with 2 to 10dimethylsiloxy units.

The treatment composition can comprise two or more sets of modifiedcolloidal particles, wherein the colloidal particles form a non-smoothsurface coating on a substrate surface at least after the compositionhas been applied to the substrate and has substantially dried or set.The composition includes at least a first and a second set of colloidalparticles, each of said first and second sets of colloidal particlesincluding a plurality of colloidal particles, each having an averagesize of colloidal particles. In each of the first and second sets ofcolloidal particles, the average particle size of the first set ofcolloidal particles is greater than the average particle size of saidsecond set of colloidal particles. Moreover, the composition includes agreater number of colloidal particles in the second set of colloidalparticles than the number of colloidal particles in the first set ofcolloidal particles.

In one embodiment, the ratio of average particle sizes between the firstset of colloidal particles and the second set of colloidal particles isat least about 1.1:1. In another preferred embodiment, the ratio theaverage particle size of the first set of colloidal particles to theaverage particle size of the second set of colloidal particles is atleast about 1.5-20:1. In a further embodiment, the composition comprisesa ratio of the number of colloidal particles of the second set ofcolloidal particles to the number of particles of the first set ofcolloidal particles is at least about 2:1. In another embodiment, thecomposition comprises a ratio of the number of colloidal particles ofthe second set of colloidal particles to the number of particles of thefirst set of colloidal particles is about 10-1000:1. In anotherembodiment of the invention, the average particle size of the first setof colloidal particles is about 15-2000 nm, and the average particlesize of the second set of colloidal particles is about 1-200 nm. In afurther embodiment, the average particle size of the first set ofcolloidal particles is about 15-200 nm, and the average particle size ofthe second set of colloidal particles is about 1-40 nm.

Hydrophobically Modified Silica

In one non-limiting embodiment of the invention, a plurality ofcolloidal particles are modified so as to include one or more alkylchains. As can be appreciated, colloidal particles can be modified toinclude other or additional types of hydrocarbon chains (e.g., alkanechain, alkene chain, aryl chain, etc.). The hydrocarbon chains can besubstituted (e.g., hydrogen substituted with a halogen, anotherhydrocarbon chain, etc.) or non-substituted chains. The alkyl chains,when used, are believed to increase the hydrophobicity of the modifiedcolloidal particles. Typically, smaller colloidal particles and/orshorter alkyl chains result in improved packing of the colloidalparticles, which in turn can also or alternatively increase thehydrophobicity of a coating of colloidal particle containing material ofthe present invention on a surface. The alkyl chains can be saturatedchains or unsaturated chains. The colloidal particles in the colloidalparticle containing material of the present invention can all bemodified or a portion of the colloidal particles can be modified.

The modified colloidal particles can be modified in the same ordifferent way. For instance, one set of colloidal particles can includeone type of hydrocarbon chain and another set of colloidal particles caninclude a longer and/or different type of hydrocarbon chain. The lengthof each of the alkyl chains on one or more colloidal particles is up toabout a 30 carbon chain; however, larger lengths can be used in someapplications. When the alkyl chain is too large, the alkyl chain canbegin to interfere with the proper formation of the non-smooth surfaces.In another and/or alternative non-limiting embodiment, the averagelength of an alkyl chain on colloidal particles that have been modifiedto include alkyl chains is about a 1-24 carbon chain. In onenon-limiting aspect of this embodiment, the length of each of the alkylchains on one or more colloidal particles is about a 1-18 carbon chain.In another non-limiting aspect of this embodiment, the length of each ofthe alkyl chains on one or more colloidal particles is about a 2-16carbon chain. In still another non-limiting aspect of this embodiment,the length of each of the alkyl chains on one or more colloidalparticles is about a 3-16 carbon chain. In another yet non-limitingaspect of this embodiment, the length of each of the alkyl chains on oneor more colloidal particles is about a 3-8 carbon chain. In stillanother and/or alternative non-limiting embodiment of the presentinvention, the colloidal particle containing material of the presentinvention includes colloidal silica particles that have been modified toinclude one or more hydrocarbon chains (e.g., alkyl chains, etc.). Themodification of silica to include hydrocarbon chains such as alkylchains is known in the art, thus will not be described herein.

Two or more sets of colloidal particles in the colloidal particlecontaining material of the present invention can include differentlengths and/or types of hydrocarbon chains. The different types and/orlengths of hydrocarbon chains can be used to alter the size of themodified colloidal particles. The modified size of the colloidalparticles alone or in combination with the types and/or lengths ofhydrocarbon chains can be used to alter the hydrophobicity of thecolloidal particle containing material of the present invention. Forinstance, colloidal particles that are generally the same size, can bedifferentiated in size by modifying at least a portion of the colloidalparticles by use of different types and/or lengths of hydrocarbonchains. The effect of the different sized particles can be the same orsimilar to when different sized colloidal particles are used asdiscussed above. As can be appreciated, different sized colloidalparticles can also be modified by different types and/or lengths ofhydrocarbon chains. In essence, the differentiated particle size of thecolloidal particles can be obtained by 1) using different sizedcolloidal particles, 2) using the same sized colloidal particles butmodifying a portion of the colloidal particles with one type and/or sizehydrocarbon chain, 3) using the same sized colloidal particles butmodifying a portion of the colloidal particles with one type and/orsized hydrocarbon chain and modifying another portion of the colloidalparticles with a different type and/or sized hydrocarbon chain, 4) usingdifferent sized colloidal particles and modifying a portion of thecolloidal particles with one type and/or sized hydrocarbon chain, or 5)using different sized colloidal particles but modifying one sized set ofcolloidal particles with one type and/or sized hydrocarbon chain andmodifying another sized set of colloidal particles with a different typeand/or sized hydrocarbon chain.

It is also envisioned to provide a method for forming a hydrophobiccoating on a substrate by providing a formulation that includes asolvent and a first and second set of colloidal particles. Each of thefirst and second sets of colloidal particles includes a plurality ofcolloidal particles, and the average particle size of each of the firstand second sets of colloidal particles are such that the averageparticle size of the first set of colloidal particles is greater thanthe average particle size of the second set of particles. Further, thecomposition if formulated such that the second set of colloidalparticles comprises a greater number of colloidal particles than thenumber of colloidal particles in the first set of colloidal particles.The hydrophobic coating is then applied to the surface of a substrateand is allowed to at least partially set or dry on said surface of saidsubstrate. In this regard, the formulation creates a non-smooth coatingon the surface of the substrate that is formed by the at least first andsecond sets of colloidal particles.

Suitable hydrophobically modified fumed silica particles that may beused in the present invention include silica particles that have beenhydrophobicized by any means known in the art. In some embodiments ofthe invention, the silicon dioxide utilized is a colloidal silicondioxide. Colloidal silicon dioxide is a generally fumed silica preparedby a suitable process to reduce the particle size and modify the surfaceproperties. A common process in the art to modify the surface propertiesis to produce fumed silica, for example by production of the silicamaterial under conditions of a vapor-phase hydrolysis at an elevatedtemperature with a surface modifying silicon compound, such as silicondimethyl dichloride. Such products are commercially available from anumber of sources, including Cabot Corporation, Tuscola, Ill. (under thetrade name CAB-O-SIL™) and Degussa, Inc., Piscataway, N.J. (under thetrade name AEROSIL®).

Suitable hydrophobically modified fumed silica particles include, butare not limited to, those commercially available from DegussaCorporation, Parsippany, N.J., as designated under the R Series of theAEROSIL® and AEROXIDE® LE trade names. The different AEROSIL® R andAEROXIDE® LE types differ in the kind of hydrophobic coating, the BETsurface area, the average primary particle size and the carbon content.The hydrophobic properties are a result of a suitable hydrophobizingtreatment, e.g., treatment with at least one compound from the group ofthe organosilanes, alkylsilanes, the fluorinated silanes, and/or thedisilazanes. Commercially available examples include AEROSIL® R 202,AEROSIL® R 805, AEROSIL® R 812, AEROSIL® R 812 S, AEROSIL® R 972,AEROSIL® R 974, AEROSIL® R 8200, AEROXIDE® LE-1 and AEROXIDE® LE-2.

Other silica materials are also suitable when hydrophobically modifiedby use of hydrophobizing materials capable of rendering the surfaces ofthe silica particles suitably hydrophobic. The suitable hydrophobizingmaterials include all those common in the art that are compatible foruse with the silica materials to render their surfaces suitablyhydrophobic. Suitable examples, include, but are not limited to theorganosilanes, alkylsilanes, the fluorinated silanes, and/or thedisilazanes. Suitable organosilanes include, but are not limited toalkylchlorosilanes; alkoxysilanes, e.g., methyltrimethoxysilane,methyltriethoxysilane, ethyltrimethoxy-silane, ethyltriethoxy-silane,n-propyltrimethoxysilane, n-propyltriethoxysilane,i-propyltrimethoxysilane, propyltriethoxysilane, butyltrimethoxysilane,butyltri-ethoxysilane, hexyltrimethoxy-silane, octyltrimethoxysilane,3-mercaptopropyl-trimethoxysilane, n-octyltriethoxy-silane,phenyltriethoxysilane, polytriethoxysilane; trialkoxyarylsilanes;isooctyltrimethoxy-silane;N-(3-triethoxysilylpropyl)methoxy-ethoxyethoxy ethyl carbamate;N-(3-triethoxysilylpropyl)methoxyethoxyethoxyethyl carbamate;polydialkylsiloxanes including, e.g., polydimethylsiloxane; arylsilanesincluding, e.g., substituted and unsubstituted arylsilanes; alkylsilanesincluding, e.g., substituted and unsubstituted alkyl silanes including,e.g., methoxy and hydroxy substituted alkyl silanes; and combinationsthereof. Some suitable alkylchlorosilanes include, for example,methyltrichlorosilane, dimethyldichlorosilane, trimethylchloro-silane,octylmethyldichlorosilane, octyltrichlorosilane,octadecylmethyldichlorosilane and octadecyltrichlorosilane. Othersuitable materials include, for example, methylmethoxysilanes such asmethyltrimethoxysilane, dimethyldimethoxysilane andtrimethylmethoxysilane; methylethoxysilanes such asmethyltriethoxysilane, dimethyldiethoxysilane and trimethylethoxysilane;methylacetoxysilanes such as methyltriacetoxysilane,dimethyldiacetoxysilane and trimethylacetoxysilane; vinylsilanes such asvinyltrichlorosilane, vinylmethyldichlorosilane,vinyldimethyl-chlorosilane, vinyltrimethoxysilane,vinylmethyldimethoxysilane, vinyldimethyl-methoxysilane,vinyltriethoxysilane, vinylmethyldiethoxysilane andvinyldimethyl-ethoxysilane.

Disilazanes which can be employed in the present invention as processingaids are well known in the art. Suitable disilazanes, include forexample, but are not limited to hexamethyldisilazane,divinyltetramethyldisilazane andbis(3,3-trifluoropropyl)tetramethyldisilazane. Cyclosilazanes are alsosuitable, and include, for example, octamethylcyclotetrasilazane. It isnoted that the aforementioned disilazanes and cyclosilazanes typicallyhave the basic formula (I) and (II) described above. Thus, thesedisilazanes and cyclosilazanes can be used as either or both ashydrophobizing material for hydrophobically modifying fumed silicaparticles and as a processing aide in forming the pre-dispersionmentioned supra.

Suitable fluorinated silanes include the fluorinated alkyl-, alkoxy-,aryl- and/or alkylaryl-silanes, and fully perfluorinated alkyl-,alkoxy-, aryl- and/or alkylaryl-silanes. Examples of fluoroalkyl silanesinclude, but are not limited to those marketed by Degussa under thetrade name of Dynasylan. An example of a suitable fluorinatedalkoxy-silane is perfluorooctyl trimethoxysilane.

Coating

In a further embodiment of the present invention, a protective coatingis formed on a receptive surface by deposition of a treatmentcomposition comprising: (a) 0.05 to 5.0 percent by weight of a pluralityof hydrophobically modified fumed silica particles having a medianparticle size of between 100 and 4,000 nanometers; (b) 99.95 to 5percent by weight of a volatile solvent; (c) optionally, 0.001 to 5percent by weight of a suspending agent; (d) optionally, 0.001 to 5percent by weight of a functional adjunct; and (e) optionally, inbalance to 100 percent by weight if present, a propellant.

The protective coating comprises a non-smooth coating on the receptivesurface at least after the treatment composition has been applied to thereceptive surface and has substantially dried or set. The non-smoothcoating on the receptive surface includes valleys and peaks and anaverage height between the valleys and peaks of about 1-2500 nm. Theprotective coating can be substantially transparent or non-transparent.

Another and/or alternative non-limiting object of the present inventionis the provision of a formulation that includes colloidal particles thatform a surface structure on an applied surface which surface structureincludes elevations and depressions that are at least partially formedby colloidal particles.

Still another and/or alternative non-limiting object of the presentinvention is the provision of a formulation that includes colloidalparticles that form a surface structure on an applied surface whichsurface structure includes elevations and depressions that are at leastpartially formed by different sized colloidal particles.

The non-smooth surface coating that is formed when the composition isapplied to the substrate surface includes valleys and peaks. Thenon-smooth surface coating results in an average height between thevalley and peaks of about 1-2500 nm. In another embodiment, thenon-smooth surface on the substrate surface includes valleys and peakshaving an average height between the valley and peaks of about 2-100 nm.

Process Equipment

Suitable equipment for effectively dispersing the hydrophobicallymodified fumed silica particles of the present invention include anykind of device which is capable of applying high enough shear forces toa concentrated particulate slurry and thus being effective at decreasingthe average particle size distribution of particles within the slurrydown to 100 to 4,000 nanometers where initial particle sizes range fromabout 1 to 1,000,000 nanometers can be employed according to the methodsof the present invention. Suitable examples include, but are not limitedto, mixers and/or dispersers based on the rotor stator principle such asthe L4RT type available from Silverson Machines, Waterside at CheshamBucks, England. Further suitable examples are mixers using dissolver ordispenser blades, such as the CV type available from Dispermat(BYK-Gardner, Geretsried, Germany), and/or the H-Trieb 4REB/L modelavailable from Heynau Getriebe, Landshut, Germany. Effective dispersingcan also be achieved with a horizontal mill, one suitable example beingthe MH2P type from OKK USA Company, Glendale Heights, Ill.

Durability Agent

A durability agent may optionally be included in the process and/ortreatment compositions of the present invention. When included, onepossible embodiment is to include the durability agent during theprocessing step. Suitable durability agents may be selected from thegroup of alkoxysilanes of the general formula (III)

R⁵ _(a)Si(OR⁶)_(4-a)  (III)

wherein R⁵ is a straight or branched, saturated or unsaturated alkylchain group of from 1 to 16 carbon atoms, optionally substituted withflourine atoms, hydroxyl, amino, mercapto, or epoxy groups, R⁶ is analkyl chain of 1 to 2 carbon atoms, a is 1 or 2; or selected form thegroup of alkyl-modified linear or cyclic polydimethylsiloxanes of thegeneral formulas (IV) and (V)

(CH₃)₃SiO[(CH₃)₂SiO]_(n)[(CH₃)R⁷SiO]_(o)Si(CH₃)₃  (IV)

—[(CH₃)₂SiO]_(p)[(CH₃)R⁷SiO]_(q)-(cyclo)  V)

wherein R⁷ is an alkyl chain group of from 6 to 24 carbon atoms, n isfrom 1 to 100, o from 1 to 40, p from 0 to 7, q from 1 to 7, providedthat the sum (p+q) is at least 3. Additional durability agents suitablefor use herein include those previously disclosed in U.S. Pat. Pub. No.2004/0213904A1.

The level of durability agent employed herein is typically between 0.1and 10 percent by weight of the total weight of the composition.

Volatile Solvent

A volatile solvent is employed in the inventive process and/or treatmentcompositions in the capacity of a liquid carrier for methods ofdelivering and effectively applying the treatment compositions to areceptive surface in a manner capable of forming a functional protectivecoating on the surface.

Suitable volatile solvents are selected from the group of aromatic,branched, cyclic, and/or linear hydrocarbons with 2 to 14 carbon atoms,optionally substituted with flourine or chlorine atoms, monovalentlinear or branched alcohols, aldehydes or ketones with 1 to 6 carbonatoms, ethers or esters with 2 to 8 carbon atoms, linear or cyclicpolydimethylsiloxanes with 2 to 10 dimethylsiloxy units, and mixturesthereof. Examples of suitable volatile solvents include, but are notlimited to, n-propane, n-butane, n-pentane, cyclo-pentane, n-hexane,cyclo-hexane, n-heptane, isododecane, kerosene, methanol, ethanol,1-propanol, isopropanol, 1-butanol, dimethylether, diethylether,petroleum ether and ethylacetate, octamethyltrisiloxane, marketed underthe trade name Dow Corning 200 Fluid lest,decamethylcyclo-pentasiloxane, marketed under the trade name Dow Corning245 (available from Dow Chemical), TEGO® Polish Additiv 5 (availablefrom Degussa), perfluorinated solvents, and other halogenated materialssuch as chlorinated solvents are also suitably employed where their useis appropriate.

Additional solvents that may be employed include those organic solventshaving some water solubility and/or water miscibility, and at least someability to couple with water or moisture that may be present or becomeincorporated into the inventive treatment compositions throughprocessing, packaging and during application. These are generally addedin addition to the more volatile solvent, although they may be employedalone as well as in any suitable combination or mixture capable ofstabilizing the dispersion of the hydrophobically modified silicaparticles during processing, packaging, storage and use.

Suitable organic solvents include, but are not limited to, C1-6alkanols, C1-6 diols, C1-10 alkyl ethers of alkylene glycols, C3-24alkylene glycol ethers, polyalkylene glycols, short chain carboxylicacids, short chain esters, isoparafinic hydrocarbons, mineral spirits,alkylaromatics, terpenes, terpene derivatives, terpenoids, terpenoidderivatives, formaldehyde, and pyrrolidones. Alkanols include, but arenot limited to, methanol, ethanol, n-propanol, isopropanol, butanol,pentanol, and hexanol, and isomers thereof. Diols include, but are notlimited to, methylene, ethylene, propylene and butylene glycols.Alkylene glycol ethers include, but are not limited to, ethylene glycolmonopropyl ether, ethylene glycol monobutyl ether, ethylene glycolmonohexyl ether, diethylene glycol monopropyl ether, diethylene glycolmonobutyl ether, diethylene glycol monohexyl ether, propylene glycolmethyl ether, propylene glycol ethyl ether, propylene glycol n-propylether, propylene glycol monobutyl ether, propylene glycol t-butyl ether,di- or tri-polypropylene glycol methyl or ethyl or propyl or butylether, acetate and propionate esters of glycol ethers. Short chaincarboxylic acids include, but are not limited to, acetic acid, glycolicacid, lactic acid and propionic acid. Short chain esters include, butare not limited to, glycol acetate, and cyclic or linear volatilemethylsiloxanes.

Organic solvents that are less volatile can optionally be included incombination with the more volatile solvent for the purpose of modifyingevaporation rates. Suitable examples of less volatile organic solventsare those with lower vapor pressures, for example those having a vaporpressure less than 0.1 mm Hg (20° C.) which include, but are not limitedto, dipropylene glycol n-propyl ether, dipropylene glycol t-butyl ether,dipropylene glycol n-butyl ether, tripropylene glycol methyl ether,tripropylene glycol n-butyl ether, diethylene glycol propyl ether,diethylene glycol butyl ether, dipropylene glycol methyl ether acetate,diethylene glycol ethyl ether acetate, and diethylene glycol butyl etheracetate (all available from ARCO Chemical Company).

Volatile solvent is typically present at a level of between 99.95 to 5wt. % of the finished treatment composition.

Propellant

Propellants which may optionally be used in conjunction with theinventive treatment compositions are those well known and conventionalin the art and include, for example, a hydrocarbon, of from 1 to 10carbon atoms, such as n-propane, n-butane, isobutane, n-pentane,isopentane, and mixtures thereof; dimethyl ether and blends thereof aswell as individual and mixtures of chloro-, chlorofluoro- and/orfluorohydrocarbons- and/or hydrochlorofluorocarbons (HCFCs). Usefulcommercially available compositions include A-70 (Aerosol compositionswith a vapor pressure of 70 p.s.i.g. available from companies such asDiversified and Aeropress) and Dymel 152a (1,1-difluoroethane fromDuPont). Also suitable as propellants are compressed gases such ascarbon dioxide, compressed air, nitrogen, and possibly dense orsupercritical fluids may also be used, either alone or in combination,and alternatively in combination with other propellant types.

In dispensing applications employing a propellant, the inventivetreatment composition is dispensed by activating the actuator nozzle ofan aerosol type container onto the area in need of treatment, and inaccordance with the application manner as described herein, the area istreated when the inventive treatment composition is deposited onto thesurface, the propellant normally dissipating during the dispensing stepso that minimal residue of the propellant remains associated with theinventive treatment composition as it impinges the surface to betreated. The nature of the atomization by extremely rapid propellantdissipation is believed to produce extremely fine droplets of theinventive treatment compositions to aid in producing an even spraypattern and allow deposition of a uniform and consistent film of theliquid inventive treatment composition onto the surface, althoughalternative non-propellant assisted delivery means may also be suitablyemployed.

If a propellant is used, it will generally be in an amount of from about1 wt. % to about 75 wt. % of the aerosol formulation. Generally, theamount of a particular propellant employed should provide an internalpressure of from about 20 to about 150 p.s.i.g. at 70° F. in order toprovide good atomization and delivery of the inventive treatmentcompositions.

Suspending Agent

Suspending agents may optionally be included in the inventive treatmentcompositions to improve the suspension and/or dispersion properties ofthe inventive compositions. Suspending agents when employed, mayfunction to improve the suspension and dispersion properties of thehydrophobically modified fumed silica particles, other solid particulateadditives, and other optional agents and functional adjuvants includedin the treatment composition. They are generally employed at levelssufficient for stabilization and so that when present, the level ofusage does not negatively impact the beneficial transparent propertiesof films provided by use of the inventive treatment compositionscontaining them.

Suitable suspending agents include polymers and surfactants, andcombinations thereof.

Polymer type suspending agents include anionic, cationic and nonionicpolymers. Examples include, but are not limited to vinyl polymers suchas cross linked acrylic acid polymers with the CTFA name Carbomer,cellulose derivatives and modified cellulose polymers such as methylcellulose, ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl methylcellulose, nitro cellulose, sodium cellulose sulfate, sodiumcarboxymethyl cellulose, crystalline cellulose, cellulose powder,polyvinylpyrrolidone, polyvinyl alcohol, guar gum, hydroxypropyl guargum, xanthan gum, arabia gum, tragacanth, galactan, carob gum, guar gum,karaya gum, carrageen, pectin, agar, quince seed (Cyclonia oblongaMill), starch (rice, corn, potato, wheat), algae colloids (algaeextract), microbiological polymers such as dextran, succinoglucan,pulleran, starch-based polymers such as carboxymethyl starch,methylhydroxypropyl starch, alginic acid-based polymers such as sodiumalginate, alginic acid propylene glycol esters, acrylate polymers suchas sodium polyacrylate, polyethylacrylate, polyacrylamide, andpolyethyleneimine.

Other optional suspending agents include anionic, cationic, nonionic,amphoteric and zwitterionic surfactants. Examples of surfactants thatare useful as particle suspending agents, which can be categorized asacyl derivatives, include long chain amine oxides, and mixtures thereof.Exemplary suspending agents of this type are described in U.S. Pat. No.4,741,855. Additional suitable suspending agents include ethylene glycolesters of fatty acids, preferably having from about 16 to about 22carbon atoms. Also suitable are the ethylene glycol stearates, both monoand distearate; alkanol amides of fatty acids, for example stearicmonoethanolamide, stearic diethanolamide, stearic monoisopropanolamideand stearic monoethanolamide stearate; long chain acyl derivativesincluding long chain esters of long chain fatty acids, for example,stearyl stearate and cetyl palmitate; long chain esters of long chainalkanol amides, for example, stearamide diethanolamide distearate,stearamide monoethanolamide stearate); and glyceryl esters, for example,glyceryl distearate, trihydroxystearin, a commercial example of which isThixin® available from Rheox, Inc. Also suitable are long chain acylderivatives, ethylene glycol esters of long chain carboxylic acids, longchain amine oxides, and alkanol amides of long chain carboxylic acids.

Other long chain acyl derivatives suitable for use as suspending agentsinclude N,N-dihydrocarbyl amido benzoic acid and soluble salts thereofincluding for example the sodium and potassium salts;N,N-di(hydrogenated) C16, C18 and tallow amido benzoic acid species ofthis family, which are commercially available from Stepan Company(Northfield, III., USA).

Examples of suitable long chain amine oxides for use as suspendingagents include longer chain alkyl dimethyl amine oxides, for example,stearyl dimethyl amine oxide.

Other suitable suspending agents include primary amines having a fattyalkyl moiety having about 12 or more carbon atoms, examples of whichinclude palmitamine or stearamine; and secondary amines having two fattyalkyl moieties each having at least about 12 carbon atoms, examples ofwhich include dipalmitoylamine or di(hydrogenated tallow)amine. Stillother suitable suspending agents include di(hydrogenated tallow)phthalicacid amide, and crosslinked maleic anhydride-methyl vinyl ethercopolymer.

In addition, other polymer and surfactant materials known in the art mayalso be suitably employed in the inventive treatment compositionsprovided that they do not negatively impact the performance of theprotective films when applied to a receptive surface.

When included, the suspending agent is typically employed at a level ofabout 0.001 to 5 wt. % of the finished treatment composition, or at alevel that does not impact the desirable beneficial optical propertiesof the films provided by use of the present invention.

Functional Adjunct

Treatment compositions, methods and treatment systems of the presentinvention may optionally further include one or more functionaladjuncts. Functional adjuncts may be combined with the inventivetreatment compositions, combined during processing of the concentratedprocess materials or process compositions, or alternatively post addedor delivered simultaneously during dispensing and application of theinventive treatment compositions according to the methods and treatmentsystems described herein.

Functional adjuncts are optionally included to provide at least oneadditional beneficial property, functional and/or corollary benefit, oraesthetic enhancement to the treatment compositions, or the resultantprotective coatings provided by use of the treatments compositionsand/or treatment systems employing them. The functional property can beone that provides enhanced product properties owing to improved storagestability, and thus incorporating for example, but not limited to phasestabilizers, corrosion protection agents, dispersants, and the like,including combinations thereof for improving treatment compositionstorage properties when packaged. Additionally, functional adjuncts thatprovide enhanced dispensing properties, including for example, flowagents, atomization aids, wetting agents, spreading agents, evaporationmodifiers, solvent couplers, drying aids, azeotropic cosolvents,droplet-size modifiers, and the like, including combinations thereof forimproving the step of application wherein the treatment compositions aredispensed and applied to the targeted surface to provide the inventiveprotective properties described herein.

Further functional adjuncts may be included that provide enhancedprotective benefits and/or corollary benefits to the protective filmspresent on receptive surfaces treated by use of the inventive treatmentcompositions. Suitable functional adjuncts providing such enhancedprotective benefits and/or corollary benefits may be selected fromultraviolet light absorbers, ultraviolet light blockers, free-radicalscavengers, fluorescent whitening agents, colorants, dyes, pigments,photoactive particles, color changing dyes, color fading dyes, bleachingagents, fixative agents, perfume, fragrance, odor control agents,anti-static agents, and combinations thereof.

When included, the functional adjunct is typically employed at a levelof about 0.001 to 5 wt. % of the finished treatment composition, or at alevel that does not impact the desirable beneficial optical propertiesof the films provided by use of the present invention.

Water

Since the inventive treatment compositions described herein aregenerally non-aqueous, water is generally excluded from the composition,and materials employed, including optional functional adjuncts, areselected which are free of excessive water and/or moisture. Theinventive treatment compositions and methods of application describedherein may tolerate some water, particularly if a coupling solvent,selected from a water miscible, water soluble, and/or partially watersoluble solvent or combinations thereof, is employed as an optionalfunctional adjunct in the treatment composition. If water is present, itmay be de-ionized, industrial soft water, or any suitable grade of waterfor the particular application.

For non-aqueous treatment compositions, water is preferably limited tolevels of less than 5% by weight or volume, more preferably less than 2%by weight or volume and most preferably less than 1% by weight orvolume. When coupling solvents are employed, water may be present atsignificantly higher levels, any level being suitable provided that thelevel of water and any necessary coupling agent does not interfere withthe ability of the inventive treatment compositions to form transparent,renewable and durable surface protective coatings on the receptivesurfaces to which they are applied.

Areas of Use

The methods, treatment compositions and treatment systems employing theinventive treatment compositions and methods according to the presentinvention may be used to treat a receptive surface of a substrate,material, article, and/or object, wherein the respective surfaces arereceptive to treatment and capable of hosting the durable andnon-permanent deposited film comprising the hydrophobically modifiedfumed silica particles in the form of silica particle agglomerates onthe surface.

The treatment compositions of the present invention can be used fortreating a variety of receptive surfaces of inanimate articles,including non-porous and porous surfaces comprising automotive andhousehold materials, and their respective surfaces. Examples of suitableautomotive surfaces and articles include, but are not limited to,wheels, wheel trim, wheel covers, removable wheel covers, splash guards,car panels and painted surfaces, clear-coated car surfaces, metal,painted metal fixtures, chromed articles, bumpers, bumper stickers, bugdeflectors, rain deflectors, vinyl materials including car boots, wheelcovers, convertible tops, camper awnings, sun shades, vehicle covers,license plates, plastic articles, lens covers, signal light lenscovering, brake light lens covering, headlamp and fog light lenscovering, and the like. Examples of suitable interior automotivesurfaces include, but are not limited to, vinyl and upholstery surfaces,dashboard, dash instrument lens covering, seats, carpet, floor runners,speaker covers, and the like.

Treatment compositions of the present invention can be used on articlesand surfaces found inside and outside the home, including for example,kitchen and bathroom areas, living areas, interior and exteriorsurfaces. Suitable surfaces include both porous and non-porous surfaces,materials and substrates. Non-limiting examples of non-porous surfacesinclude metals, metal oxides, aluminum, anodized aluminum, paintedsubstrates, stainless steel, chrome, clear-coated automotive surfaces,ellastomers, vinyl, plastics, polymers, sealed wood, laminates,composites, and the like. Non-limiting examples of porous surfacesinclude fibers, textiles, non-wovens, woven materials, foam substrates,cloth, clothing, leather, upholstery, carpet, curtains, marble, granite,grout, mortar, concrete, spackling, plaster, adobe, stucco, brick,unglazed tile, tile, unglazed porcelain, porcelain, clay, wallpaper,cardboard, paper, wood, and the like.

Examples of suitable surfaces and articles found in and around a homedwelling include, but are not limited to, ceilings, walls, wallpaper,floors, counter tops, sinks, backsplashes, cabinets, wood paneling,laminates, stone, granite, marble, limestone, tile, porcelain, plastics,polymers, coated materials, caulking, grout, spackling, shower walls,shower enclosures, shower curtains including cloth, plastic andlaminated, toilets, bidets, and the like. Suitable articles andmaterials that may be treated according to the present invention furtherinclude carpet, furniture, drapes, curtains, blinds, vinyl blinds,pull-shades, rugs, upholstered items, and the like.

Surfaces and materials exterior to the home on which the presentinvention may be used include exterior walls, trim, doors, gutters,windows, screens and window coverings, and the like. Materials ofconstruction suitable for treatment include wood, painted surfaces,metal surfaces, vinyl, receptive glass, polymeric substrates, includingplastic materials, and porous materials such as adobe, clay, concrete,stone, brick, mortar, stucco, siding, and the like that are located inan exterior environment.

In an embodiment, the protective coatings of this disclosure can provideanti-corrosion properties to a receptive surface. For example, theprotective coatings may be applied to a component part to prevent orminimize corrosion of that component part. For such anti-corrosionapplications, the coating can be transparent and result in a change ofless than 3.0 Delta E units to the receptive surface measured before andafter deposition of the coating, or the coating can be non-transparentand result in a change of more than 3.0 Delta E units (e.g., 3-9 Delta Eunits) to the receptive surface measured before and after deposition ofthe coating. Coatings that result in a change of more than 3.0 Delta Eunits typically exhibit greater durability and longer lasting propertiesthan coatings that result in a change of less than 3.0 Delta E units.The coatings of this invention can be useful in applications wheretransparency is not a desired property, as well as applications wheretransparency is a desired property.

Polymeric Substrates

Articles treated according to the inventive methods and compositions asdescribed herein may be selected from those articles of constructioncomprising polymeric substrates that normally exhibit hydrophobicsurface properties in that they exhibit the tendency to collect dirtand/or bead water when water is applied to their untreated surfaces.Articles include those wholly constructed of, laminated with, and/orcoated with a polymeric substrate, film, or coating.

Polymeric substrates include condensed polymers which are rendered intomaterials of construction having at least one treatable or receptivesurface. These polymeric substrates can be in any physical form, forexample, but are not limited to, panels, molded forms, foams, sheets,solid surfaces, laminated films and coatings on a secondary substrate,and the like. The polymeric substrates may have any desired physicalproperties, for example, but not limited to, forms that aresubstantially elastic, non-elastic, flexible, compressible, oressentially rigid, and combinations thereof.

Suitable articles of the present invention include those constructs andarticles of construction typically found in and around the home andcommercial environments featuring at least one treatable surfacecomprising a hydrophobic polymeric substrate, including for example, butare not limited to, plastics, elastomers and laminates used in theconstruction of floors, tiles, panels, walls, doors, ceilings, bathtubs,shower stalls, sinks, cabinets, countertops, fixtures, and the like.

Suitable polymeric substrates and articles constructed thereof, include,but are not limited to polyethylene terephthalate, polyamide,polyurethane, polyester, polyethylene, polyvinyl chloride (PVC),chlorinated polyvinylidene chloride, polyacrylamide, polystyrene,polypropylene, polycarbonate, polyaryletherketone, poly(cyclohexylenedimethylene cyclohexanedicarboxylate), poly(cyclohexylene dimethyleneterephthalate), poly(cyclohexylene dimethylene terephthalate)glycol,polyetherimide, polyethersulfone, poly(ethylene terephthalate)glycol,polyketone, poly(oxymethylene), polyformaldehyde, poly(phenylene ether),poly(phenylene sulfide), poly(phenylene sulfone), polystyrene,polysulfone, polytetrafluoroethylene, polyurethane, poly(vinylidenefluoride), polyamide, polyamide thermoplastic elastomer, polybutylene,polybutylene terephthalate, polypropylene terephthalate, polyethylenenaphthalate, polyhydroxyalkanoate, polyacrylate,poly(methyl)-methacrylate (PMMA), polytrimethylene terephthalate,polyvinylidene chloride and combinations thereof.

Suitable polymeric substrates and articles constructed thereof furtherinclude copolymeric materials made of one or more monomers selected fromacrylate, acrylonitrile, butadiene, ethylene, formaldehyde, maleicanhydride, melamine, methacrylate, methyl methacrylate, phenol,propylene, styrene, urethane, and vinyl acetate. Specific examples ofthese copolymeric materials (and their common industrial acronyms)include acrylonitrile:butadiene:styrene (ABS),acrylonitrile:styrene:acrylate (ASA), ethylene:propylene (E/P),ethylene:vinyl acetate (EVAC), methylmethacrylate:acrylonitrile:butadiene:styrene (MABS),methacrylate:butadiene:styrene (MBS), melamine:formaldehyde (MF),melamine:phenol:formaldehyde (MPF), phenol:formaldehyde (PF),styrene:butadiene (SB), styrene:maleic anhydride (SMAH), styrene:acrylonitrile (SAN), styrene:butadiene (SBC), vinyl acetate:ethylenecopolymer (VAE), and combinations thereof.

Also suitable are polymeric substrates and articles constructed ofthermoplastic elastomers including, but not limited to, copolyesterthermoplastic elastomer (TPC), olefinic thermoplastic elastomer (TPO),styrenic thermoplastic elastomer (TPS), urethane thermoplastic elastomer(TPU), thermoplastic rubber vulcanisate (TPV), neoprene, vinyl, siliconeelastomer, and combinations thereof.

Methods of Use

Treatment compositions of the present invention are generally applied ina manner so as to deposit fine droplets of the liquid compositioncomprising the colloidally dispersed hydrophobically modified fumedsilica particles in a volatile solvent as a continuous coating upon areceptive surface such that the droplets completely cover the surface toeffectively merge to form a thin continuous liquid film upon initialdeposition. This first manner of application is generally preferred fora single treatment application. Alternatively, the liquid treatmentcompositions can be applied in a manner to uniformly coat the area ofthe surface to a nearly complete extent as an array of fine dropletsarranged in high density, but finely separated so as not to form acontinuous liquid film. In this latter method of application, dependingon the degree of surface protection desired, a single application, ormultiple repeated applications of the inventive treatment compositionscan be applied to produce the desired level of surface coverage.

Following this application step of applying the liquid treatmentcomposition to the surface, the volatile solvent is left to evaporate inthe second step of the process, effectively leaving a deposited film ofparticles in the form of silica particle agglomerates than isessentially transparent. The evaporation of the volatile solvent resultsin a thin, macroscopically uniform and essentially transparent film onthe receptive surface that is detachable and renewable, and exhibitsexcellent dirt-repellency, and also water-repellency owing to high.water contact angles sufficient to effect beading water incident on thesurface so that the deposited film exhibits provides soil- andwater-repellency, and the ability of the soiled surface to beself-cleaning, and readily cleanable with only the application of water.

Without being bound by theory, it is believed that the evaporation ofthe volatile solvent of the present invention provides for some relativeordering and separation of the particles across the area of the treatedsurface following application, without significant clumping orassociation between the particles and/or agglomerates, which likelyresults in a mono-layer of deposited particles having favorable opticalproperties owing to the absence of significant scattering centers due tootherwise unfavorable clustering of agglomerates. Thus, treatmentcompositions of the present invention tend to form essentiallytransparent films on the treated surfaces that are nearly invisible tothe human eye, even when applied to particularly glossy or highlyreflective surfaces where surface defects or other coatings in the artare readily discernable. Without being bound by theory, it is furtherbelieved that the volatile solvent serves to effect reversibleattachment of the particles to the receptive surfaces by weaker,non-covalent binding forces by enabling the particles during theevaporation step to settle onto the surfaces in their lowestenergetically favorable binding states with maximum surface contact.Owing to the extremely small particle sizes, and the ability of theparticle agglomerates to adopt the most favorable positions duringsolvent evaporation, binding forces owing to hydrophobic-hydrophobicinteractions and van der Waals forces are sufficient to enable thehydrophobically modified silica particles to bind tightly enough tosuitably receptive surfaces to effectively resist displacement evenunder flowing water and/or air, yet be readily removed when desired bymoderate means.

Thus, the films produced by the treatment compositions, treated articlesbearing such films according to the methods of the present inventionprovide films that are detachable and may be readily removed by physicalmeans, such as by abrasion, rubbing or wiping using some appropriatephysical tool or wiping article and/or by chemical means, such as by useof a surface active agent, dispersant and/or solvent, or some suitablecombination of these to overcome the relatively weak binding energies ofthe particles and displace them from the surface. It is noted that wateralone under typical temperatures and pressures, such as rain water,splashed water and a moderate water spray using a home garden hose, andfurther, even water with significant soil load and contaminants present,is not effective in displacing the films of the present invention, thusenabling them to act as detachable but durable protective coatings onreceptive surfaces and substrates that favorably repel dirt, and owingto their hydrophobic nature and high water contact angles arewater-repellent and capable of being cleaned of any adhering soil ordirt using water alone. The treated surfaces also exhibit a surprisingability to repel and resist the adhesion of dry soils and particulatematter, such as brake-dust and household dust, and the surfaces bearingthe protective films according to the present invention can be cleanedusing a gentle stream of air alone, or if a vertical surface the use ofa gentle tapping, shaking or slight percussive motion to displaceparticulate soils. Thus, receptive materials treated according to themethods and treatment compositions of the present invention exhibitdirt-repellency, are self-cleaning, and their favorable repellencyproperties provide easy cleaning using water alone. Further, treatedmaterials exhibit easier cleaning and easier next-time cleaning in thatnon-removable and/or excessive soil load that may adhere to the film areprevented from associating with the underlying surface, and thus aremore readily removed from the surface during a cleaning step employing acleaning agent, such as a surfactant solution, owing to the films beingdetachable in nature and thus acting as a removable sacrificial barrierin protecting the treated surface from soil adhesion and build-up, whilestill providing self-cleaning characteristics to the surface. Surfacesthus cleaned to remove a previously applied protective film, may then bereprotected by a fresh application of the present inventive treatmentcompositions to restore the self-cleaning and easier next time cleaningbenefits. Thus, the surface treatment and resulting protective benefitis infinitely renewable in that the surface may subsequently beretreated periodically, or at any desired interval without any harm ordegradation of the original surface.

In addition, an inventive protective coating on a previously treatedsurface may be renewed by repeated application of the inventivetreatment compositions, without prior removal of the protective coating,even if the coating is partially worn away or damaged. Generally, it isdesirable to remove a prior coating, particularly if the surface becomesdamaged and/or excessively soiled between treatments, but this is not arequirement. Without being bound by theory, it is believed thatreapplication of the inventive treatment compositions to a previouslytreated surface, owing to the reintroduction of the solvent carrier andan additional fresh aliquot of the hydrophobic silica agglomerates,results in sufficient resuspension and redistribution of the inventivematerials across the surface in a manner that essentially renews theprotective coating while preventing excessive build-up that wouldotherwise diminish the superior optical properties exhibited by theinventive treatment compositions.

Application Means

Application of the inventive treatment compositions to a receptivesurface may be achieved by use of an application device employing anysuitable means known in the art capable of producing a fine distributionof fine liquid droplets and directing them to the surface to be treated.The application device can be an aerosol or non-aerosol device.Treatment compositions can be sprayed using any suitable type ofsprayer. One suitable type of sprayer is an aerosol pressurized packageusing a propellant. If an aerosol sprayer is used, it can use anysuitable type of propellant. The propellant can include hydrocarbonpropellants, or non-hydrocarbon propellants. A non-hydrocarbonpropellant may include, but is not limited to a compressed and/orliquefiable gas. Suitable compressed gases include, but are not limitedto compressed air, nitrogen, inert gases, carbon dioxide, etc., andsuitable liquefiable volatile materials include, but are not limited topropane, butane, pentane, and materials selected from hydrocarbons,fluorocarbons, perfluorocarbons, chlorofluorocarbons, and mixturesthereof.

In one embodiment, a pressurized aerosol package is employed, using theliquid treatment compositions of the present invention, optionallypressurized by use of a suitable pressurized gas, compressible liquidand/or liquid propellant, and/or gaseous propellant or combinationsthereof, in combination with a dispensing valve capable of suitablydispensing the liquid treatment composition in the form of a pluralityof fine droplets.

Suitable aerosol delivery includes the Truspray® system (available fromBoehringer Ingelheim-Steag microParts, Dortmund, Germany) which employscapillary atomization technology to deliver fine atomization withreduced propellant and solvent levels, enabling more concentratedcolloidal dispersions and/or thickened treatment compositions accordingto the present invention to be suitably dispensed.

Also suitable are application devices and/or dispensing devices notrequiring the use of a pressurization means and/or propellant means.

One suitable example disclosed in U.S. Pat. No. 6,708,852 to Blakedescribes a mechanically pressurized dispensing system that offers analternative to chemically pressurized aerosol dispensers. The system isfitted over a standard container holding a liquid product, and includesa dip tube assembly to draw liquid into the dispensing head assembly,where the contents are released through the dispensing head assembly,via the nozzle and valve. A twist of the threaded cap raises a piston,thereby opening a charging chamber within the dispensing head assembly.This creates a vacuum with the resulting suction pulling the product upthrough the dip tube to fill the charging chamber. Twisting the cap inthe opposite direction lowers the piston in a down stroke, which closesthe charging chamber, forcing the product into the expandable elasticreservoir where it is then discharged through the nozzle.

Also suitable are applicator devices in which the container encloses theliquid treatment composition present in a separate pouch, either foiledor foil-less bag, that is surrounded by propellant within the containerand surrounding the inner sealed pouch. Examples include those disclosedin U.S. Pat. No. 6,196,275 to Yazawa et al., U.S. Pat. No. 4,308,973 toIrland, and U.S. Pat. No. 5,730,326 to Kaeser describing a rechargeablecontainer. U.S. Pat. App. 2003/0102328 to Abplanalp et al. describes anaerosol container lacking a return spring and product dip tube. For someapplications, a dip tube may still be appropriate. The valve may havemultiple product delivery openings. The container may use a propellantdriven piston to dispense the product or the product may be in acollapsible, flexible bag.

U.S. Pat. No. 5,111,971 to Winer describes a pressurized liner-sleeveassembly that can be fitted with an aerosol valve, and requires nopropellant.

Elimination of the chemical propellant can reduce or eliminate volatileorganic content (VOC) to allow compliance with various state and federalregulations designed to reduce green-house gas emissions. Alternativesto chemically pressurized dispensers include various mechanicallypressurized models that obtain prolonged spray time by storing a chargewithout the use of chemical propellants. Such “stored charge” dispensersinclude types that are mechanically pressurized at the point ofassembly, as well as types that may be mechanically pressurized by anoperator at the time of use. Stored charge dispensers that arepressurized at the point of assembly often include a bladder that ispumped up with product. Examples include those described in U.S. Pat.Nos. 4,387,833 and 4,423,829.

Stored charge dispensers that are pressurized by an operator at the timeof use typically include charging chambers that are charged by way ofscrew threads, cams, levers, ratchets, gears, and other constructionsproviding a mechanical advantage for pressurizing a product containedwithin a chamber. This type of dispenser is generally be referred to asa “charging chamber dispenser.” Many ingenious charging dispensers havebeen produced. Examples include those described in U.S. Pat. No.4,872,595 of Hammett et al., U.S. Pat. No. 4,222,500 of Capra et al.,U.S. Pat. No. 4,174,052 of Capra et al., U.S. Pat. No. 4,167,941 ofCapra et al., and U.S. Pat. No. 5,183,185 of Hutcheson et al., which areexpressly incorporated by reference herein.

U.S. Pat. App. 2005/0035213 to Erickson et al. describes an ultrasonicspray coating system comprising an ultrasonic transducer with sprayforming head, integrated fluid delivery device with air and liquidsupply passage ways, support brackets and an ultrasonic power generator.The ultrasonic transducer consists of an ultrasonic converter thatconverts high frequency electrical energy into high frequency mechanicalenergy. The converter has a resonant frequency. A spray forming head iscoupled to the converter and is resonant at the same resonant frequencyof the converter. The spray forming head has a spray-forming tip andconcentrates the vibrations of the converter at the spray-forming tip.The separate passage ways for air and the liquid supply allows thetreatment compositions to remain separated from potential contaminantsuntil used. The ultrasonic transducer can produce a fine mist or a sprayas the transducer is adjusted. Additional ultrasonic spray devices aredescribed in U.S. Pat. App. 2004/0256482 to Linden and U.S. Pat. No.6,651,650 to Yamamoto et al., which describes an ultrasonic atomizer forpumping up a liquid from a liquid vessel by an ultrasonic pump andatomizing the liquid by passing it through a mesh plate formed to havemultiplicity of minute holes. The device can be controlled forautomatic, manual, or intermittent operation.

Another non-limiting example is the TrueSpray™ (TTP Group, TheTechnology Partnership) and TouchSpray™ (ODEM affiliates of TTP, BespakPLC and PARI GmbH, Germany) atomization devices which both employ amicrodroplet generating system based on a perforated membrane that isvibrated at selected frequencies to convert a continuous flow of anatomizable liquid composition on one side of the membrane into a finespray of liquid droplets emanating from the opposite side. The systememploys an electrical means using either a battery or other electronicpower supply and a circuit to control the vibrational frequencies,amplitudes and duration of membrane oscillation in order to controlliquid flow and dispensing rates as well as droplet size, distribution,velocity and atomization rate. A favorable property of this applicationmeans is the tendency of the system to produce smaller liquid dropletsizes on the order of 10 to 100 microns in diameter, with a majority ofthe liquid droplets of a size within several standard deviations of themean liquid droplet size, thus producing a homogeneous distribution offine liquid droplets of uniform size, which would be capable of forminga more uniform surface film of applied material when used to deposit theinventive treatment compositions onto a receptive surface.

Also suitable are electrostatic applicators, which may be employed as adelivery means that combines any suitable atomization means with adispenser capable of imparting a unipolar charge on the dispensed liquiddroplets, which may be selected to be net positive or net negativedepending on the conditions desired and target substrate. Imparting aunipolar charge to the dispensed droplets acts to disperse them duringatomization, as the like-charged droplets tend to repel one another sothat coherence of the spray pattern of the plurality of droplets ismaintained while the droplets are in flight. The unipolar charge,suitably selected, may also act to accelerate, attract and/or adhere thecharged droplets onto either a neutral, polarizable or oppositelycharged surface to effectively increase deposition efficiency andfurther decrease overspray and droplet bounce from the target surface,as well as producing more uniform films on the surface.

Treatment System (Kit)

The inventive treatment compositions, suitably packaged in a dispensingand/or applicator means for direct application to a receptive surface,may be combined in the form of a treatment system (treatment kit orkit). The treatment system may further contain instructions for use ofthe inventive treatment compositions, including a list of suitablesurfaces and substrates that may be treated, application techniques andapplication instructions illustrating use of and most suitable means ofapplying the compositions to surfaces, pre-cleaning instructions, dryinginstructions, and post-treatment cleaning instructions, and the like.

Generally, it is desirable to treat a surface that has been previouslycleaned so as to form a first protective coating on a cleaned receptivesurface. This is typically done for most surfaces by washing with adetergent, hard surface cleaner, soap or some similar cleaning agentfollowed by either rinsing with water and allowing to dry, or wiping drydirectly, or wiping dry after rinsing with water. Generally, it isdesirable to remove all trace residue of water, cleaning agent and otheradherent materials before treatment. The inventive treatmentcompositions may be applied to damp or slightly wetted surfaces, butgenerally a substantially dry surface, such as one free of adherentwater droplets, to which the inventive treatment compositions areapplied provides for the most appealing aesthetic surface treatment.Thus, treatment systems according to the present invention mayoptionally include a drying article, such as for example, but notlimited to an absorbent material, a drying aid, and/or combinationsthereof. Examples of suitable absorbent materials that may be used as adrying article include, but are not limited to a woven, non-woven,sponge, polymeric foam, microfiber, paper towel, paper pad, tissue orother similar absorbent article or wiping article capable of effectivelyabsorbing and/or removing water from a wetted surface prior toapplication of the inventive treatment compositions. Other alternativedrying articles include drying devices. Examples of suitable dryingdevices include for example, but are not limited to, a compressed gassource, infrared heat generating device, forced air device, such as apowered fan, combinations thereof, and the like.

Preparation of Treatment Compositions

Treatment compositions according to the present invention may beprepared by a variety of methods well known in the art depending on thequantity and scale desired. For the purpose of consistency in preparingsmall batches for testing and evaluation, inventive treatmentcompositions were prepared using process compositions, i.e. concentratedhydrophobically modified fumed silica dispersions as indicated, producedaccording to the inventive process described herein, and then furtherprocessed in the following manner described below suitable for obtainingquantities of 100 to 5,000 grams of a finished or ready-to-use treatmentcomposition. First, a major aliquot, or total desired level of thevolatile solvent is weighed into a plastic vessel, optionally with aremaining minor aliquot of the volatile solvent retained in order tolater rinse the walls of the mixing vessel, if desired. Stirring is thenbegun using a conventional motorized mixer using a mechanical stirringrod of suitable size, operated at a speed of about 300 to 400 r.p.m.sufficient to create a smooth vortex without splashing of the volatilesolvent. Addition of the optional dispersing agent, and/or addition ofthe optional durability agent, if any, is performed by slowly addingeach separately in turn and mixing sufficiently to achieve a uniformsolution and/or suspension of the agents in the volatile solvent,generally following about 5 to 10 minutes mixing duration. The processcomposition is then added slowly to the solution, and after completeaddition, any remaining aliquot of the volatile solvent added in such amanner as to rinse any adhering particles on the mechanical stirring rodand/or sides of the mixing vessel into the bulk liquid. The mixing speedis generally maintained at 400 r.p.m., but may optionally be increasedto about 1000 r.p.m. if desired, and stirring continued for a timesufficient to produce a homogeneous dispersion of the particles, whichcan be as short as a minute or so, or longer if additional materials areto be added. Alternatively, the optional dispersing agent, and/oroptional durability agent may be added at this stage of the mixing toproduce a final treatment composition.

This approach produces suitable treatment compositions of colloidaldispersions of the hydrophobically modified fumed silica particlesaccording to the present invention in a volatile solvent, which may thenbe combined with a suitable applications means to provide for suitabledispensing onto a target surface. In one embodiment, for example, thetreatment compositions may be packaged into a suitable aerosol container(i.e. a conventional pressurized spray can with pin hole nozzle) as anapplication means combined in the form of a treatment system, andoptionally combined with a propellant or compressible gas to provide forsuitable dispensing by atomization.

In another embodiment, treatment compositions may be processed furtherwith addition of, and/or dilution with additional volatile solvent,and/or additional optional suspending agent(s), and/or additionaloptional functional adjuncts, and/or optional propellant prior topackaging or use. In yet another alternative embodiment, the colloidaldispersion of the hydrophobically modified fumed silica particles may bepackaged or associated with a non-aerosol applicator for dispensing bysuitable means not requiring direct pressurization and/or use of apropellant.

For testing purposes, treatment compositions prepared from the processcompositions described herein comprising dispersions of thehydrophobically modified fumed silica particles in the volatile solventwere applied using the PreVal™ system commercially available fromPrecision Valve (New York, N.Y.).

Preparation of Samples for Particle Size Analysis

Particle size analysis of the hydrophobically modified fumed silicaparticles was performed following application to a treated surface byuse of scanning electron microscopy (SEM) to image and evaluate particlesize, distribution and coverage of the particles present in-situ on thesurface. Representative substrates were tested, including plastic andmetal surfaces, by employing flat plastic and aluminum test panels,respectively, of approximately 1″×1″ size that are carefully cleanedwith anhydrous isopropanol and dried prior to use. Coated test panelsare prepared by first covering one-half of the panel (approximately½″×1″ portion) with heavy stock paper or suitable barrier that will notwet through or overspray during application of test formulations, whichare then sprayed manually in essentially the same manner as used inapplying a spray paint to a surface, by evenly spraying the treatmentcompositions onto the test panel surface using a smooth uninterruptedlinear motion during spraying, with the nozzle located approximately 6″from the surface, with the spraying action commencing a short time priorto reaching the one edge of the test panel and continuing for a shorttime after passing the second edge of the test panel in order to producea uniform coating. The treated panel is allowed to dry with the partialcover paper attached, and then mounted onto a carrier sheet, e.g. athicker piece of paper stock by using double sticky tape, and the samplestored under a dust cover prior to imaging to preserve the treatedsurface.

The surface morphology of the test panels coated with the inventivetreatment compositions were examined using a Hitachi S-4300SE SEM(Hitachi USA) operated at an accelerating voltage of 2 kilovolts (KV).The test panels were dried at room temperature and no additional coatingwas performed prior to the examination.

Results of the SEM imaging are shown in the accompanying FIGS. 1 and 2.In FIG. 1, a black test panel was treated with a conventional Lotuseffect coating formulation prepared according to the methods describedin U.S. Pat. Pub. No. 2004/0213904, corresponding to comparative Example21 as referenced herein. By eye, the panel treated by the comparativematerial appeared visually hazy and the SEM image shows a generallyuneven (non-homogenous) surface covered by small particles presumed tobe larger silica agglomerates and/or clumps of agglomerated material. InFIG. 2, a black test panel was treated with the inventive treatmentcomposition (Example 15) employing means of application according to themethods of the present invention, but otherwise prepared, treated andevaluated in an identical manner as the first test panel. By eye, thepanel was extremely glossy and reflective, no noticeable film orhaziness being apparent on the surface under normal lighting conditions.The SEM image in FIG. 2 reveals an extremely smooth and uniform film ofparticulate materials on the surface of the panel, evidence of a veryisotropic and homogeneous surface morphology. The scale of both SEMimages is about 200 μm, corresponding to an effective magnification ofabout 250×.

Atomic Force Microscopy

Atomic force microscopy (AFM) was used to determine the extent andnature of the renewable surface modification effects according to thematerials, treatment compositions and methods of application of thepresent invention. The AFM technique allows virtual imaging of thesurface at a scale fairly comparable to that of the applied depositedmaterials so that surface topography can be ascertained to a high degreeof precision. AFM images were obtained using a Digital InstrumentsNanoscope III in non-contact mode with Olympus Tapping Etched SiliconProblem Aluminum-coated (OTESPA) sensing tips. Images were acquired fromthe center of each one inch square segment of panel. Although phase datawas simultaneously acquired, no significant phase difference in thetopography were detected, so images were generated without includingthis factor. Photomicrographs of the AFM data generated images arepresented herein with appropriate vertical height scales indicated bythe relative intensity of the image at the indicated coordinates, scaledfrom black (0) to white (1) on a relative basis with respect to therelative vertical height range indicated in the key insert accompanyingthe photomicrograph, and the horizontal length scale length is indicatedon the borders in units of micrometers (um). FIG. 3 shows typicaltopographical images obtained on a treated black paint panel aftertreatment with a treatment composition applied according to the presentinvention, compared to FIG. 4 of an untreated black paint panel.

Preparation of Coated Paint Panels

Treatment compositions of the present invention were applied to avariety of surfaces for testing and evaluation, using representativematerials selected for convenience of testing under controlledconditions including a clear coated black painted metal rectangular testpanel obtained from ACT Laboratories Co., Hillsdale, Mich., designatedAPR41841, Batch 50505412, having an exceptionally high gloss surfaceowing to clear-coating finish R10CG060Z UreClear. Test panels were firstthoroughly cleaned with isopropyl alcohol (IPA), washed with a soap andwater solution, and finally rinsed with IPA, rinsed with de-ionizedwater, wiped dry with a dry lint-free paper towel. Visual inspection ofeach panel was performed to insure cleanliness and panels were handledby the edges to prevent fingerprints from marring the surface. Selectedportions of the panel were masked to produce control and treatmentareas, the middle roughly ⅓ area section being masked by use of a foldedpaper covering the center of the test panel or temporary barrier whensprayed to prevent overspray. Samples were placed in a holder so thatthey could be sprayed while in a vertical orientation. After masking,the exposed right and left side sections were treated by spraying testformulas using the PreVal™ sprayer system, held about 8 to 10 inchesabove the panel surface with spraying times of about 3 seconds, in aconsistent overlapping spray pattern with motion from top to bottom ofthe panel, repeated consistently for every panel in the set, whichusually included three sets of panels and four replicates per set pertreatment composition under evaluation. Following spraying, test panelsare either dried at 80° C. for 15 minutes (accelerated drying), followedby at least 5 minutes of cooling time, or allowed to dry at roomtemperature or about 70° F. overnight or until dry by appearance(typically 5-30 minutes depending on the surface and up to one to twohours for heavy applications on some non-porous surfaces).

The first set of panels was used for evaluation of hydrophobic surfacemodification with respect to water repellency (“Roll Off Test”),appearance evaluation with a haze meter instrument (“Chrome Test”), andgloss-meter instrument, and durability testing under repeated waterrinse conditions (“Durability Test”). The second set of panels were usedto evaluate self-cleaning soil repellency characteristics measured bothqualitatively by visual rankings using trained evaluators and/orquantitatively using a combined gloss-meter and colorimeter instrument.

Roll Off Test

To measure the ability of treated surfaces to repel water, contact anglemeasurements and visual evaluation of the behavior of a water dropletwas performed. A single drop of tap water (roughly 0.05 mL) was appliedto the test panel surface held in a horizontal position. Contact angleswere measured using an N.R.L. Model C.A. 100-00 goniometer (Rame-Hart,Mountain Lake, N.J.). Surface behavior of the water droplet was observedwhile the panel was moved and rocked gently while held by hand in agenerally horizontal position, and a rating score assigned to thetreated panel based on the behavior of the water droplet as describedbelow:

Rating Description of Visual Behavior 1 “Marble on a surface” - waterdroplet rolls easily 2 Rolls easily, but sticks occasionally 3 Rollsfreely but sticks some times 4 Rolls freely but sticks more often 5Remains mostly in place with hardly any movement 6 Water droplet remainsfixed in place (untreated surface)

Roll Off Height Test

In addition to visually assessing roll off behavior, a “roll off height”measurement was performed to determine the height of inclinationrequired for water to roll off from a panel following a surfacetreatment to be evaluated. Panels were prepared using the same approachas described in the preceding Roll Off Test herein.

Panels to be evaluated are then placed on a flat or elevated flatsurface in a horizontal position, with one side of the panel, and ifrectangular in shape this being one of the short sides of therectangular panel, placed in close proximity to a vertically positionedscaled ruler placed perpendicular to the flat or elevated surface suchthat the height of the selected edge as it is displaced from thehorizontal position can be readily measured by comparing the edge to themarkings on the scale.

With the panel in the initial horizontal position, from about three tofive independent drops of water (about 0.1 mL each) are gently pipettedonto the panel in an approximately straight line located approximatelyparallel to the selected edge and located approximately 1 inch from theselected edge. The panel is then lifted so as to elevate the selectededge of the panel in an upward vertical direction slowly and smoothly toprevent any undesirable motions, until all of the water droplets “breakfree of the surface” and/or begin to move or roll down the inclinedsurface of the panel. The height at which the drop begins to roll off isobtained from the scale, being the “Roll Off Height”, and generallyexpressed in centimeters (cm).

Any residual liquid (spotting or trailing) after the drops have rolledoff is noted. Additional replicates or measurements of the Roll OffHeight are obtained by rotating the test panel 180 degrees and repeatingthe test again.

Chrome Test

All appearance measurements under identical conditions were taken eitherbefore and after treatment, or taken from treated and untreated (masked)sections of the test panel, with the difference between thesemeasurements calculated to determine changes as a result of thetreatment or soiling test employed. Colorimetric, gloss and hazemeasuring instrumentation and techniques can be employed to demonstratethe surprisingly transparent nature of the surface protective films andcoatings formed onto receptive surfaces by means of employing theinventive treatment compositions.

Colorimeter measurements were performed using a Minoltaspectrophotometer, Model CM-508D, Serial No. 15711032, with anilluminating/viewing geometry selected to compensate for specularreflection, SCE (specular component excluded), obtained from KonicaMinolta Photo Imaging Inc. Instruments Systems Division, Mahwah, N.J.

Measurements before and after treatment or soiling were taken asdescribed above, although tests can be done in different order to enablesequential testing against the various test methods for convenience. Allmeasurements are generally replicates of duplicate or additional trialsthat are then averaged, differences before and after treatment beingreported at Delta E, which is the total color difference between thesample and a reference sample, or alternatively the initial untreatedand final post-treated sample after treatment was applied. To determinethe major contribution to the Delta E value, Delta L and thecolorimetric “a” and “b” parameters were examined and Delta L was foundto best represent, and be most sensitive to changes in the visuallyappearance of treated materials, likely owing to the colorimetric “L”parameter being the parameter that tracks total neutral shade valuesfrom pure black (L=0) to pure white (L=100) in the absence of any colorcontributions. Similar measurements were also employed to measure therelative influence on Delta E and Delta L following application andremoval of soil to provide an approach to measuring comparative soilremoval. Visual evaluation of the surfaces held at a reflective angle toa light source (a suitable example being normal overhead fluorescentroom lighting, incandescent lamp and outdoor sunlight) was alsoperformed to judge aesthetic characteristics of treated surfaces, inparticular appearance associated with common visual descriptorsincluding: “uneven” and/or “streaky”, “hazy”, cloudy” and/or “dull”,“pearlescent” and/or “rainbow effect”, and “clear” and/or “glossy”.Here, both “pearlescent” and “rainbow effect” refer to the tendency ofthin transparent films, depending on their thickness, regularity ofthickness and the substrate to which applied, produce interference anddiffraction effects upon reflection of incident white light which areperceived as a plurality of colored patterns and colored bands,respectively.

Haze measurements were performed using a Haze Gloss Meter, Model No.4606, available form BYK Gardner, Silver Spring, Md., U.S.A. calibratedwith a haze-gloss standard reference No. 195829312 providing a haze setpoint value corresponding to H′(20°)=463. Haze unit measurementsobtained were uncompensated (indicated as “nc”) values determined aftercalibration. Delta Haze units corresponded to the difference in measuredHaze units obtained by subtraction of haze unit values obtained beforeand after treatment of a chromed panel, or between an untreated controlpanel and a treated panel, or between an untreated and treated portionof the same panel, as indicated. Generally, Delta Haze unit measurementsusing the same panel before and after treatment and other testprocedures as described herein are preferred for improved accuracy, witha multiple number of replicate readings taken across the surface toenable an average value to be calculated.

Delta Haze unit measurements were made on the treated surfaces tocorrelate the level of haze associated with the typical ability of thehuman eye to discern noticeably perceptible visual change in the surfaceappearance of treated substrates viewed under normal room lighting. Ahighly polished mirror finished reflective chromed test panel wasselected as a preferred surface for the purposes of testing anddemonstrating the advantageous optical properties of surface protectivefilms provided by use of the instant treatment compositions, as thechrome surface showed a high sensitivity to changes in surfaceappearance and measured haze parameters. The chrome test panels, 4″×8″in size are designated SAE-1010 CR with ⅛″ hole for suspension, ChromePlated Steel, available from Metaspec, Inc., San Antonio, Tex. Thus theChrome Test, conducted to provide a Delta Haze unit measurement ontreated chrome, provides a convenient means of measuring thesurprisingly improved transparent protective films produced by theinventive treatment compositions.

Generally, the inventive treatment compositions when applied to thepolished chrome test panels produced transparent and nearly invisiblesurface coatings that demonstrated the beneficial protective propertiesas described herein. Haze measurements confirmed that Delta Haze unitvalues of below around 250 as measured according to the Chrome Testmethodologies described hereinabove are readily achievable by use of theinventive compositions, these Delta Haze unit values corresponding to achange in the measured haze value wherein the level of haze produced onthe surface is barely, if at all perceptible to the human eye.

Substantivity and Durability Test

Substantivity testing was also performed to determine the ability of thetreated surfaces to maintain their beneficial properties followingtreatment, and the durability of the beneficial properties followingchallenge by soils, dirt, water, mechanical abrasion and action ofcleaning solutions. These substantivity and durability tests provide ameasure of the inventive treatment compositions utility for treatedinterior and exterior surfaces, and materials likely to be exposed to avariety of typical environmental challenges.

Panels previously used for the Roll Off Test may be employed, or newlyprepared panels, placed and held in an approximately vertical position.For substantivity testing, panels are sprayed over an approximately3″×6″ area, using an electrosprayer charged with regular tap water(Febreze Power Sprayer, carefully cleaned and rinsed with water beforeuse, distributed by the Procter and Gamble Company, Cincinnati, Ohio)for 15 seconds of continuous spray, measured using a timer.

Following spraying, the surface of the panel is visually evaluated todetermine the tendency of any water drops to remain on the surface,which would be indicative of a loss of the protective benefit, comparedto an untreated control panel. The number of drops and surfaceappearance of the panels following the rinsing are collectively assigneda visual substantivity grading score being an integer from 0 to 10,using the following scale as guidance, with intermediate assignmentspossible:

Rating Description of Visual Behavior (Water Adhesion) 10 No observedwater droplets 7 Small number of water droplets 5 Some water droplets 3Numerous water droplets 1 Appearance similar to untreated control 0Appearance worse than untreated control

Durability Test

Durability testing is performed in a similar manner as the substantivitytest described hereinabove, with the substantivity test procedurerepeated a multiple number of times (cycles) until a visual gradingscore of approximately 5 is observed, at which point the number ofcycles is recorded as the Durability Test Score. This Durability TestScore essentially represents the number of water rinses over which theprotective benefit may be observed, with a higher number of cyclesrepresenting both increased substantivity (the effect) and persistenceof effect (duration) of the surface protective benefit at an acceptablelevel of performance (about 5 on the substantivity visual gradingscale). Durability Test Scores of at least 1 are suitable forsacrificial surface protective coatings that will provide durabilityfollowing at least one rinse event using water to remove incidentalsoil, dirt and grime from a protected surface to which the inventivetreatment compositions are applied. Higher durability scores are moresuitable for detachable, yet more durable surface coatings that canprovide multiple rinse cleaning cycles using water. A DurabilityDuration value (in units of seconds) can also be calculated bymultiplying the total number of cycles determined according to thedurability test (Durability Test Score) times the individual spray timeused (15 seconds per spray in the test method) to determine a DurabilityDuration time for the inventive films present on a treated surfaceaccording to the methods described herein.

Self Cleaning Test (Qualitative)

Self cleaning performance testing (designated “SCL Test”) is done todetermine the ability of treated panels to be cleaned of adhering soil,dust, grime and the like following simple mechanical tapping or rinsingby water alone (soil-repellency and self-cleaning performance, andeasier cleaning performance). Treated panels are first exposed to a soilladen environment, or may be soiled artificially to mimic such exposurein the following manner: Treated panels and control panels arepositioned on a flat or inclined surface, depending on the surface to bemodeled or for worst case testing positioned in a horizontalorientation. Powdered soil of choice is shaken onto the panels toproduce a thin uniform coating, the panel is re-orientated into avertical position so that excess (non-adherent) soil will fall away. Tosimulate brake-dust as a test soil, brake fines obtained fromreplacement brake pads as described below were combined to obtain a dryfree flowing finely powdered dust. The brake dust thus obtained wasplaced into a large cheese shaker can with fine holes on the top,inverted and applied evenly across the test panel surfaces by hand.

Brake-dust test soil was prepared by finely grinding down the top threepurchased brands of brake pads obtained from Grand Auto, a nationalretailer with branches throughout the United States, corresponding toHonda Accord front new pads #45022-S84-A02, Honda Accord rear new pads#43022-SY8-A01, VW Jetta front new pads #1SATZ 1-J0698 151 J, VW Jettarear new pads #1 SATZ 1 J0698 451 D, Ford Taurus front new pads#2F1Z-2001-AA, and Ford Taurus rear new pads # F8DZ-2200-AA. All padswere individually ground down to a fine dust, which was then sievedthrough a 325 mesh screen on a conventional Rotap™ machine to collectonly the fines below that mesh size. For an approximately 30 gramportion of finished brake-dust test soil, about 3 grams each of the backbrake pad fines and about 7 grams each of the front brake pad fines (thefront pads wearing faster during typical use) were combined to produce arepresentative test soil that closely resembled that observed on actualvehicle wheels produced during normal operation.

Once the soiled panel is prepared, it is rated using the description ofvisual behavior scale presented herein below, and is then mounted ineither an inclined or vertical position. In dry soil resistance testing,the panel is lightly tapped once and the appearance evaluated todetermine dry soil repellency/resistance. In a wet soil resistance test,the panel is sprayed with water in a manner as described above in theSubstantivity Test Method, using tap water in the electronic sprayeroperated for about 15 seconds over the entire surface. For either test,a duplicate replicate panel is treated in an identical manner andreserved as a control for subsequent comparisons. After the test panelsare treated, visual surface appearance of the panels are assigned a SelfCleaning Performance score using the following scale as guidance, eitherin reference to a treated but unsoiled panel (unsoiled control) that isrinsed according to the procedure above, or in reference to an untreatedbut soiled panel. The visual scale employed is as follows:

Rating Description of Visual Behavior (Dry or Water Rinse Test) −3most/all soil removed (resembles unsoiled control) −1 slightly less soilsticks or remains 0 no change (untreated soiled panel control) +1slightly more soil remains +3 most/all soil remains

Self Cleaning Test (Quantitative)

Quantitative measurements of the self-cleaning performance may beperformed by conducting haze test measurements on panels employed asdescribed above in the “SCL Test” procedure. Haze measurements ofuntreated panels, treated panels, tapped soil-treated panels posttesting, and soil-treated rinsed panels and rinsed treated panels areobtained by measuring haze at 20° using a Haze-Gloss BYK Gardner Model4606 instrument, and averaging four readings per test panel or duplicatereadings on at least three replicates panels.

Uniformity Appearance Rating (Qualitative)

A surface appearance uniformity ranking (designated “Chrome Test”) areperformed by measuring treatments applied to a glossy and reflectivesurface such as a mirror or high gloss chromed metal substrate. Aftertreatment and drying times as described hereinabove, the highlyreflective substrates are view by eye and a qualitative visual scoreassigned based on general appearance and uniformity of the surface overabout a 3.5″×4″size treatment area.

Rating Description of Visual Behavior 6 white haze - significant cloudyand/or dull appearance 5 some hazy appearance 4 uneven appearance and/orstreaks observed 3 some distortion but mostly clear with high glossappearance 2 slight distortion with overall clear and glossy appearance1 no distortion or visual change (resembles untreated surface)

Ratings are assigned according to the above scale and closest appearanceto the description of visual behavior noted, using these actual textualdescriptions for judges to consider when viewing and rating the panels.

General Components of Inventive Process Compositions

Applicants have determined the shear rate dependent viscosity of theinventive process compositions (at various ranges of silica content anddisilazane) as well as prior art compositions. From this study, it wasapparent that the amount of disilazane had no influence on the flowbehavior in a concentration range between 0.5-3.0%. This supports thefinding in Table 1 presented hereinbelow that the amount of disilazanehas only a minor impact on the achieved median particle size.

Applicants further note that increasing the amount of silica (5-15%) hada dramatic impact on the viscosity. Doubling of the concentration from5% to 10% raises the viscosity by approximately one order of magnitude.Increasing the concentration to 15% silica raises the viscosity by anadditional half an order of magnitude.

Additionally, the general flow behavior is dramatically influenced bythe amount of silica. A particle load of 5% can be regarded as a verylow concentration since the flow behavior is that of an ideal (i.e.,Newtonian) liquid. At a concentration of 15% silica, however, adecreasing viscosity with increasing shear rate can be observed thatincreases again at high shear rates (dilatant peak). These resultssupport the finding in Table 1 presented hereinbelow that the amount ofsilica has a dramatic impact on the achieved median particle size.

EXAMPLES Process Compositions

Examples A through OO in Table 1 are representative embodiments ofmaterials prepared in the form of process compositions according to theprocesses of the present invention. Example H is a comparative exampleprepared in a manner outside the scope of the present invention.

Example A

A quantity of 10.0 g of hexamethyldisilazane (DYNASYLAN® HMDS) wasdissolved in 140 g of decamethylcyclopentasiloxane (TEGO® Polish Additiv5, also designated as siloxane “D 5”). 50.0 g of a commerciallyavailable, hydrophobized fumed silica with a BET surface area of 220m²/g (AEROSIL® R 812 S) was slowly dispersed in this solution withgentle stirring at 2,000 r.p.m. After all fumed silica had been added,the mixing speed of the Dispermat (single rotating shaft, outfitted withsaw-tooth blade proportional to mixing vessel where blade is half thediameter of vessel) was increased to 10,000 r.p.m. and kept operating atthis speed for 15 min.

Examples B-OO

Preparation of examples B through OO follows the same procedure as forexample A except using otherwise specified parameters as shown in Table1 below.

TABLE 1 Particle Size Process AEROSIL ® DYNASYLAN ® TEGO ®Distribution⁽¹⁾ Composition R 812 S HMDS Polish Additiv 5 Stirrer speedTime (median) Example wt. % wt. % wt. % r.p.m. min. nanometer InventiveA 25.0 5.0 70.0 10,000 15 304 B 25.0 0.5 74.5 10,000 5 283 C 25.0 5.070.0  5,000 5 1,925 D 25.0 0.5 74.5  5,000 15 2,115 E 25.0 0.5 74.5 5,000 5 2,106 F 10.0 5.0 85.0  5,000⁽²⁾ 15 3,328 G 10.0 0.5 89.5 5,000⁽²⁾ 5 3,771 OO 17.5 2.75 79.75  7,500⁽²⁾ 10 2,851 Comparative H5.0 — 93.0⁽³⁾  5,000⁽²⁾ 15 41,265 ⁽¹⁾Particle size distribution analysiswas performed with a Horiba LA 910 (use of 1.0 micron polystyrenedispersion as calibration standard, measurement of sample dispersionsdiluted with isopropyl alcohol and with Relative Refractive Index =1.10). This instrument measures the size and distribution of particlessuspended in liquid using laser diffraction. ⁽²⁾Examples F, G, H and OOwere unable to be processed at 10,000 r.p.m. ⁽³⁾Example H additionallycontains 2 wt. % of TEGOPREN ® 6814, an alkyl-modifiedpolydimethylsiloxane, as a durability agent and thus is a representativeexample of the process compositions obtained by following the processdisclosed in U.S. Pat. Pub. No. 2004/0213904A1.

Examples I through PP are examples of process compositions obtained byfurther diluting some of the process compositions in Table 1 with TEGO®Polish Additiv 5.

TABLE 2 Process Composition (Diluted) Example⁽¹⁾ I J K L M N PPComponent wt. % wt. % wt. % wt. % wt. % wt. % wt. % Process Composition20.0 — — — — — — A Process Composition — 20.0 — — — — — B ProcessComposition — — 20.0 — — — — C Process Composition — — — 20.0 — — — DProcess Composition — — — — 50.0 — — F Process Composition — — — — 50.0— G Process Composition 28.57 OO TEGO ® Polish 80.0 80.0 80.0 80.0 50.050.0 71.43 Additiv 5 ⁽¹⁾All diluted process compositions have an activesilica level of 5 wt. %.

By comparing Delta Haze values in Table 14 with particle sizes of thecorresponding process compositions, it can be concluded that a particlesize of approximately 4,000 nm or less is necessary to achieve DeltaHaze values of 250 or less which was found to be the Haze value fromwhich the coatings of the present invention start to be perceived as avisible film by the human eye on a highly polished chrome test substrateaccording to the methods described hereinabove. Table 1 shows thatseveral parameters of different weighting play a role in order toachieve a targeted particle size of 4,000 nm or less. It can beconcluded from Table 1 that the concentration of silica (AEROSIL) in theprocess compositions is by far the most important factor and that aconcentration of 10 wt. % seems to be a lower practical limit. With 5wt. % for example (Comparative example H) a more than tenfold largermedian particle size is obtained. It became also obvious that theviscosity of the process composition during mixing is critical and needsto be in a defined range (see also chapter hereinabove on “GeneralComponents of Inventive Process Compositions”). On the one hand, theprocess liquid needs to have a high enough viscosity for adequate energytransmission throughout the bulk solution to produce the requisite shearforces needed to effectively reduce particle size to the targeted medianrange. On the other hand, the process liquid must not be too viscous inorder to be still processable in the mixing equipment.

It was surprisingly found that these counteracting effects during theprocess can be balanced by the use of a disilazane derivative. Theimpact of hexamethyldisilazane, as one representative embodimentaccording to the present invention, on the rheological behavior ofhighly concentrated silica dispersions is shown in FIG. 5. FIG. 5 showsthat a dispersion with 25 wt. % silica and without hexamethyldisilazane(Process Composition U) exhibits a yield point indicated by G′>G″, whichmeans it shows a solid-like behavior, whereas a dispersion with 25 wt. %silica and with 5 wt. % hexamethyldisilazane (Process Composition R)does not have a yield point. Process composition U demonstrates that itwas basically possible to process a dispersion of silica at 25 wt. %without a disilazane derivative, but more effort was required to getthis amount of silica incorporated into the solvent, and the viscositywas too high for proper processing. The disilazane derivative not onlyhelps to keep the process viscosity at a practical level for convenientprocessing, but also helps to wet and disperse the silica in the solventmore easily. Besides the silica concentration, mixing process parameterssuch as stirrer speed and mixing duration have a significant impact onthe particle size results as well, even though they are not as importantas the silica concentration. Obviously it makes a big difference whethera disilazane derivative is present or not with respect to ease ofprocessing, but the absolute amount present seems to be of lesserimportance. In addition, it was observed that samples processed with adisilazane derivative show a retarded settlement of silica particlescompared to those samples processed without the disilazane derivatives.In summary, it was thus surprisingly found that the combination of highsilica concentration with a sufficiently high mixing speed or mixingpower is critical to achieve the desired reduction to the desirablemedian particle size range of the present invention, and that thepresence of a disilazane derivative facilitates the processdramatically.

The following examples O and P are further representative embodiments ofmaterials prepared in the form of process compositions according to theprocesses of the present invention.

Example O

A quantity of 5 kg of hexamethyldisilazane (DYNASYLAN® HMDS) wasdissolved in 70 kg of decamethylcyclopentasiloxane (TEGO® Polish Additiv5, D 5). 25 kg of a commercially available, hydrophobized fumed silicawith a BET surface area of 220 m²/g (AEROSIL® R 812 S) was added andpassed repeatedly through a horizontal mill until the desired particlesize had been achieved.

Preparation of example P follows the same procedure as for example Oexcept using otherwise specified parameters as shown in Table 3 below.

TABLE 3 Process TEGO ® Particle Size Comp- AEROSIL ® DYNASYLAN ® PolishDistribution⁽¹⁾ osition R 812 S HMDS Additiv 5 (median) Example wt. %wt. % wt. % nanometer O 15.0 3.0 82.0 174 P 15.0 1.5 83.5 296⁽¹⁾Particle size distribution analysis was performed with a Horiba LA910 (use of 1.0 micron polystyrene dispersion as calibration standard,measurement of sample dispersions diluted with isopropyl alcohol andwith Relative Refractive Index = 1.10). This instrument measures thesize and distribution of particles suspended in liquid using laserdiffraction.

Example Q is an example of a diluted process composition obtained byfurther diluting process composition O with TEGO® Polish Additiv 5.

TABLE 4 Process Composition (Diluted) Example⁽¹⁾ Q Component wt. %Process Composition O 33.3 TEGO ® Polish Additiv 5 66.6 ⁽¹⁾Correspondingto an active silica level of 5 wt. %.

The following examples R through V are representative embodiments ofprocess compositions prepared according to the methods of the presentinvention. Preparation of examples R through V follows the sameprocedure as for example A except otherwise specified parameters in thetable below. Examples A and R demonstrate the variance in the medianparticle size achievable under identical process parameters.

TABLE 5 TEGO ® Particle Size Process AEROSIL ® DYNASYLAN ® PolishStirrer Distribution⁽¹⁾ Composition R 812 S HMDS Additiv 5 speed Time(median) Example wt. % wt. % wt. % r.p.m. min. nanometer R 25.0 5.0 70.010,000 15 186 S 25.0 2.5 72.5 10,000 15 209 T 25.0 0.5 74.5 10,000 15225 U 25.0 — 75.0⁽²⁾ 10,000 15 317 V 25.0 5.0 70⁽³⁾ 10,000 15 271⁽¹⁾Particle size distribution analysis was performed with a Horiba LA910 (use of 1.0 micron polystyrene dispersion as calibration standard,measurement of sample dispersions diluted with isopropyl alcohol andwith Relative Refractive Index = 1.10). This instrument measures thesize and distribution of particles suspended in liquid using laserdiffraction. ⁽²⁾It was extremely difficult to stir in the AEROSIL ® intoTEGO ® Polish Additiv 5. ⁽³⁾In example V isododecane was used as solventinstead of decamethylcyclopentasiloxane.

Examples W through BB are examples of a diluted process compositionsobtained by further diluting some process compositions in Table 5 withTEGO® Polish Additiv 5.

TABLE 6 Process Composition (diluted) Example⁽¹⁾ W X Y Z AA BB Componentwt. % wt. % wt. % wt. % wt. % wt. % Process Composition R 20.0 — — —20.0 — Process Composition S — 20.0 — — — — Process Composition T — —20.0 — — 20.0 Process Composition V — — — 20.0 — — ABIL ® Wax 9814 — — ——  2.0 — DYNASYLAN ® OCTEO⁽²⁾ — — — — —  4.0 TEGO ® Polish Additiv 580.0 80.0 80.0 80.0 78.0 76.0 ⁽¹⁾All diluted process compositions havean active silica level of 5 wt. %. ⁽²⁾Triethoxyoctylsilane

Examples CC through HH are further representative embodiments ofmaterials prepared in the form of process compositions according to theprocesses of the present invention. They were prepared following thesame procedure as for example A.

TABLE 7 TEGO ® Process AEROSIL ® DYNASYLAN ® Polish TEGOPREN ®DYNASYLAN ® Composition R 812 S HMDS Additiv 5 6814 OCTEO Example wt. %wt. % wt. % wt. % wt. % CC 25.0 5.0 60.0 10.0 — DD 25.0 5.0 60.0 — 10.0EE 25.0 5.0 50.0 10.0 10.0 FF 25.0 — 65.0 — 10.0 GG 25.0 — 65.0 10.0 —HH 25.0 — 55.0 10.0 10.0

Examples II through NN are examples of diluted process compositionsobtained by further diluting the process compositions in Table 7.

TABLE 8 Process Composition (diluted) Example⁽¹⁾ II JJ KK LL MM NNComponent wt. % wt. % wt. % wt. % wt. % wt. % Process Composition CC30.0 — — — — — Process Composition DD — 30.0 — — — — Process CompositionEE — — 30.0 — — — Process Composition FF — — — 20.0 — — ProcessComposition GG — — — — 20.0 — Process Composition HH — — — — — 20.0 TEGOPolish Additiv 5 70.0 70.0 70.0 80.0 80.0 80.0 ⁽¹⁾Process compositionsII - KK have an active silica level of 7.5 wt. %, LL - NN an activesilica level of 5 wt. %.

Treatment Compositions Non-Porous Surface Modification

Examples of embodiments of the inventive treatment compositions suitablefor use in modification of receptive surfaces, including non-poroussurfaces and substrates, are provided in Table 9. The treatmentcompositions in these examples are prepared in the form of dilutedsilica dispersions for use with a suitable delivery means capable ofapplying the treatment compositions for surface modification of avariety of substrates and general usage on automotive, home and textilesurfaces.

TABLE 9 Treatment Composition Example 1 2 3 4 5 Component wt. % wt. %wt. % wt. % wt. % Process Composition I 1.0⁽¹⁾ 10.0⁽²⁾ 20.0⁽³⁾ 60.0⁽⁴⁾99.0⁽⁵⁾ Dow Corning DC 245 99.0 90.0 79.0 40.0 — DYNASYLANE ® — — 1.0 —1.0 OCTEO⁽⁶⁾ ⁽¹⁾Corresponding to an active silica level of 0.05 wt. % inTreatment Composition 1 ⁽²⁾Corresponding to an active silica level of0.5 wt. % in Treatment Composition 2 ⁽³⁾Corresponding to an activesilica level of 1.0 wt. % in Treatment Composition 3 ⁽⁴⁾Corresponding toan active silica level of 3.0 wt. % in Treatment Composition 4⁽⁵⁾Corresponding to an active silica level of 4.95 wt. % in TreatmentComposition 5

Additional embodiments of examples of suitable inventive treatmentcompositions for surface modification use are provided in Table 10,further including some optional functional adjuncts to provideadditional benefits to the treatment compositions and improved methodsof application onto targeted surfaces. Examples 9 and 10 arerepresentative embodiments formulated as ready-to-use propellant-basedaerosol treatment compositions.

TABLE 10 Treatment Composition Example 6 7 8 9 10 Component wt. % wt. %wt. % wt. % wt. % Process Composition J 10.0⁽¹⁾ 10.0⁽²⁾ 50.0⁽³⁾ 10.0⁽⁴⁾20.0⁽⁵⁾ Dow Corning DC 245 88.5 90.0 49.0 39.0 18.8 DYNASYLANE ® — — —1.0 — OCTEO TEGOPREN ® 6814 — — — — 0.2 Adhesion Promoter⁽⁶⁾ 0.5 — 1.0 —1.0 Paraffinic Solvent⁽⁷⁾ 1.0 — — — — Propellant⁽⁸⁾ — — — 50.0 60.0⁽¹⁾Corresponding to an active silica level of 0.5 wt. % in TreatmentComposition 6 ⁽²⁾Corresponding to an active silica level of 0.5 wt. % inTreatment Composition 7 ⁽³⁾Corresponding to an active silica level of2.5 wt. % in Treatment Composition 8 ⁽⁴⁾Corresponding to an activesilica level of 0.5 wt. % in Treatment Composition 9 ⁽⁵⁾Corresponding toan active silica level of 1.0 wt. % in Treatment Composition 10⁽⁶⁾Licocene Polypropylene 1302 metallocene derived polymer particles,with 3000 average MW, particle size of 100-275 nm, available fromClariant Corporation, Charlotte, NC. ⁽⁷⁾Odorless mineral spirits,available from Ashland Corporation, Dublin, OH. ⁽⁸⁾Proprietarypropellant mixture obtained form (ATI Corporation) capable of producingabout 50 p.s.i.g. under standard conditions and temperature whenpackaged in an aerosol container.

Further embodiments of the inventive treatment compositions prepared todetermine the dependence of properties of the protective coating oncompositional variations were explored using a design of experimentsmodel to vary component levels of the functional and optionalingredients as shown in Table 11. All treatment compositions were stableduring spraying application, and were applied using a PreVal sprayer.

TABLE 11 Treatment Composition Example⁽¹⁾ 11 12 13 14 15 16 17 18 19 2021 22 Component wt. % wt. % wt. % wt. % wt. % wt. % wt. % wt. % wt. %wt. % wt. % wt. % Process Composition W 10 — — — — — — — — — — — ProcessComposition X — 10 — — — — — — — — — — Process Composition Y — — 10 — —— — — — — — — Process Composition Z — — — 10 — — — — — — — — ProcessComposition Q — — — — 10 10 — — — — — — Process Composition L — — — — —— 10 — — — — — Process Composition K — — — — — — — 10 — — — — ProcessComposition M — — — — — — — — 10 — — — Process Composition N — — — — — —— — — 10 — — Process Composition — — — — — — — — — — — 10 PP ProcessComposition H — — — — — — — — — — 15 — (Comparative) DYNASYLANE ® — — —— —  4 — — — — — — OCTEO Dow Corning 245 90 90 90 90 90 86 90 90 90 9085 90 ⁽¹⁾All treatment compositions have an active silica level of 0.5wt. %, except comparative composition 21 which contains 0.75 wt. %active silica.

Measurements of the example embodiments were conducted according to thetest procedures described hereinabove on high gloss black clear-coatedautomotive test panels, with test data presented in Table 12, and on thehigh-gloss mirror chrome panels. Results show that a clean, untreatedblack panel is fairly hydrophobic owing to the nature of the clear-coatfinish and exhibits a water droplet contact angle of about 79.6°.Spraying of the panels according to the methods disclosed above withExample treatment compositions 2, 7, 11-14, 17, 18 and 22 providedtreated test panels all exhibiting high water contact angles sufficientto repel water. After application of the inventive treatmentcompositions 2, 7, 17, 18 and 22 to chrome panels, treated sections ofthe panels were found to be nearly identical in appearance to untreatedor control sections of the panels previously masked prior to spraytreatment to prevent deposition of the inventive treatment compositions.A six person group visually evaluated the panels (corresponding totreatment with treatment compositions 2, 7, 17, 18 and 22 according tothe “Chrome Test” appearance ranking and assigned scores on double-blindpanel sections to prevent bias, with averaged scores obtained presentedin Table 12. Results show that treatment according to methods of thepresent invention provided essentially clear surface coatings that didnot detract from observed shine of the panels, and which were notreadily discernable to the human eye, producing slight distortion or atworst some distortion while maintaining an overall clear and glossyappearance.

The ability of the treated black panels to shed water was measured usingthe roll-off height test, the height of the inclined panel from a flathorizontal position in centimeters at which water drops begin to move asshown in Table 12. Results show a tendency for the untreated panel,despite its moderate hydrophobic properties, to “pin” the water dropletin place, required a fairly large tilt angle (here in excess of 45°) andRoll-Off Height greater than 20 cm for water droplets to move. Incontrast, the treated panels exhibited the ability to bead the waterdroplets, and essentially enable the water droplets to be completelyshed from the surface with only a slight angle as the panels wereinclined to a height of less than 1 cm to about 1.5 cm, whichcorresponded to an angle of less than 10° inclination from thehorizontal.

Colorimetric test measurement of the treated panels are also shown inTable 12 as the component contributions Delta E and Delta L illustratingdifferences before and after treatment with the inventive treatmentcompositions. Changes in the control panel measured value (A) merelyreflect the instrumental uncertainty and repeatability of the test. Asdiscussed above, Delta E measurement reflect the total color differencebetween panels before and after treatment, while Delta L measurementsbest represent changes in white to black color scale “whiteness” of thepanels, an indication of any whitish film attributable to haze seen onthe panels after treatment. A higher, or positive Delta L value thencorresponds to a greater observed visual haze on the panel surface, andconversely, a lower or negative Delta L number indicates a sample isdarker than the untreated control. The inventive treatments are seen toaffect the measured color minimally, as expected from the highlytransparent nature and lack of visual indication of the film present onthe treated panel surfaces. Colorimeter measurements employing bothDelta E and Delta L components show that the inventive treatments, whichhave a minimal impact on visual appearance, correspondingly exhibit verysmall changes in both of these parameters, showing a minimal effect oncolor (total energy of reflectance, E) and negligible contribution tohaze (white component of reflectance, L).

TABLE 12 Test Results Water “Chrome Roll-Off Black Black TreatmentContact Test” Height Panel Panel Composition Angle Appearance⁽²⁾ (cm)Delta E Delta L 2 154.8° 1.8 <1 0.85 0.55 7 153.4° 2.8 <1 1.19 0.92 12153.5° — 1.5⁽³⁾ 2.68 −2.49 13 153.5° — 2.5⁽³⁾ 1.89 −0.55 14 151.2°⁽³⁾ —6 — — 17 152.6° 3.0 <1 1.10 0.87 18 154.2° 3.8 1 0.92 0.52 22 152.4° 3.71.5 1.06 0.86 Control⁽¹⁾ 79.6° 1.2 >20 0.19 −0.02 ⁽¹⁾Control isuntreated black Ford paint panel ⁽²⁾Average of six person visualappearance ratings using chrome control panel A as reference. ⁽³⁾Averageof two trials. ⁽⁴⁾Control is untreated black Ford paint panel.

The durability and self cleaning ability of surfaces treated usingseveral example embodiments was tested using treated black automotivepanels exposed to water and/or brake dust, with results presented inTable 13.

In one test, panels treated with the inventive treatment compositionswere first tested for dry dirt repellency. In a second test, the panelswere then exposed to a continuous spray of water and the time at whichthe panels first showed an indication to form adherent droplets and holdbeads of water on the surface was noted to the nearest 15 secondinterval to determine durability of the coating to a water spray.Alternatively, panels were treated with a 15 second water spray and thesurface appearance ranked by visual inspection according the visualranking scale described hereinabove to measure the appearance withrespect to any adherent water droplets. All treatment examples providedan initial benefit in readily shedding water from the surface comparedto an untreated control panel. It needs to be emphasized that alltreatment compositions in Table 13 do not contain a durability agent andyet provide good to excellent durability of the protective coating. TheSCL Brake Dust test results demonstrate the ability of the dry treatedsurface to resist adhesion of dry brake-dust without the use of anywater or cleaning action. Here, after exposure to the dry brake-dusttest soil according to the methods described herein above, a single tapwas sufficient to remove most if not all of the brake-dust present onthe black test surface treated with the inventive treatment compositionsindicated in Table 13. These test results demonstrate that a depositedfilm of hydrophobically modified fumed silica delivered via use of atreatment composition according to the present invention is capable ofproviding both wet and dry surface protective benefits, producing atreated article with the protective film deposited thereon, thatexhibits self-cleaning and easier cleaning benefits.

TABLE 13 Test Results Durability⁽¹⁾ Visual Treatment Duration AppearanceSCL Composition (sec) Ranking⁽²⁾ Brake Dust⁽³⁾  2 90 — −2  7 60 — −2 1115 10 −3 12 15 8.5 −3 13 15 9 −3 14 — — −2 15 30 — −3 17 45 — −2 18 135— −2 19 30 — −1 20 15 — −1 22 60 — −2 Control 0 0 0 ⁽¹⁾Time (in seconds)before adherent water beads observed on surface during spraying. Averageof two trials ⁽²⁾Visual Appearance Ranking for water adhesion usingappearance scale indicated hereinabove versus the control panel ⁽³⁾Drybrake-dust test, ranked on appearance scale (Dry test) using appearancescale indicated hereinabove versus the control panel

Haze Test Results

Measurements of the example embodiments were taken according to theChrome Test procedures described hereinabove on the high shine chrometest panels, with results presented in Table 14. The chrome test panelshave mirror-like finishes and any surface distortion or residue isreadily perceivable by eye, as well as instrumentally, where the Hazemeasurement technique appears to be the most suited for quantifying veryslight changes in appearance. Treatment weight recorded in Table 14reflects the amount of applied treatment composition, obtained byweighing the aerosol can containing the respective treatment before andafter controlled dispensing onto the test panel. Compositions hadcomparable level of the silica active, so that the amount of depositedsilica materials would be comparable. Application of the comparativeexample 21 produced a visually hazy and non-uniform coating on thechrome test panel that was not acceptable, and had a very large DeltaHaze unit value of 288. In comparison, inventive treatment compositions,Examples 16, 20 and 22, when applied resulted in transparent and barelyperceptible coatings on the chrome surface, all with very low Delta Hazeunit values. Example 16 produced an invisible coating that could not bediscerned by the eye, yet exhibited the full range of protectiveperformance benefits demonstrated by use of the present invention. Avariety of tests on the polished chrome revealed that an preferredtransparent surface coatings could be obtained from inventive treatmentcompositions providing a measured Delta Haze unit value of equal to orless than about 250, as determined by following the Chrome Testprocedure as described hereinabove.

TABLE 14 Haze Measurement⁽¹⁾ Median particle size of Treatment DeltaStandard Treatment base process composition Composition Haze⁽²⁾Deviation Weight⁽³⁾ (nanometers) 21 288.4 13.8 1.25 41,265 20 78.4 15.61.16 3,771 22 28.2 4.19 1.16 2,851 16 9.1 6.1 1.27 174 ⁽¹⁾Followingmethodology described hereinabove. ⁽²⁾For improved accuracy readingstaken before and after treatment on each test panel. For comparison,initial Haze values of an untreated chromed panel was about 100 units.⁽³⁾Weight of applied aerosol composition (grams).

Thus, surprisingly low Delta Haze units below around 250 before andafter treatment are demonstrated by the inventive treatment compositionseven on highly polished chrome, corresponding to a surface protectivetreatment that is transparent and nearly invisible to the eye, and yetmaintain the surface protective benefits desirable in a protective filmthat still retains effectiveness in resisting and repelling dirt, waterand soil, yet can be easily removed from the treated surfaces. The noteddecrease in observable haze corresponds to the reduced particle size,suggesting that Delta Haze values below 25, which is essentiallyinvisible, are possible when the median particle size is reduced tobelow 1000 nanometers. In addition, using colorimetric measurements,very low Delta E values below around 3.0 as measured on shiny blackmetal test panels demonstrate the ability of the inventive methods andtreatment compositions to exhibit self-cleaning capability and abilityto maintain visual appearance close to that of the treated surface priorto soiling and application of the inventive treatments, thus providing ameans for nearly invisible surface protection applicable to a widevariety of surfaces, including glossy and reflective surfaces.

Treatment of Wood Panels

The ability of an example embodiment of the inventive treatmentcomposition in a convenient aerosol form (using Example 23 below) toprovide water roll-off properties to a commercially available varnishedwood panel was tested.

Treatment Composition Example 23

Ingredient Wt. % Process Composition I 5.0 DYNASYLANE ® OCTEO 2.0 DC 24543.0 ATI Propellant 50.0

The finished wood substrate was a 3 “×6” section of tongue and groovewood flooring purchased from Home Depot, with a factory applied coatingof an OEM polyurethane finish, which being hydrophobic in natureprovides the wood with high water resistance. Half of the surface of thesample was treated by spraying with the aerosol treatment compositionfrom a distance of 6″, with the sample lying horizontally, with thesecond half was masked to prevent overspray. The sample was then allowedto dry overnight at ambient conditions.

The roll-off behavior of several water drops placed on the surface in ahorizontal position was tested, comparing the treated and untreatedregions of the surfaces. Surface behavior of multiple water droplets onthe surface were observed using and found to provide a Roll-off testrating of 2 on the treated side, and a rating of 6 on the untreatedside. Visual comparison of the treated and untreated areas provided auniformity appearance rating of 2 for the side treated with theinventive treatment compositions, which provided a clear, transparentprotective coating on the finished wood surface.

In a demonstration of the removability of the treatment, the treatedsurface was wiped three times with a dry paper towel. This dry wipingwas effective at removing the inventive treatment compositions, asevidenced by a repeated Roll-off test performed thereafter that providedequivalent ratings of 6, respectively on both the previously treated,yet cleaned, and original untreated control side of the wood panel.

Thus, the utility of the inventive treatment compositions to provideprotection of varnished decorative household surfaces against accidentalsplashes of water is demonstrated. In addition, the easy removal of thetreatment without special chemical means is also demonstrated here.

Treatment of Plastic Surfaces

The ability of the inventive treatment composition exampled above toprovide water roll-off properties to commercially available plastics wasthen tested. Plastic sheet materials, obtained from McMaster-Carr, werecut into 4″×4″ sections. Two types of materials were investigated: ablack “acrylic” plastic and a gray “PVC” (polyvinyl chloride) plastic.Each test treatment was conducted at least on duplicate samples.

The plastic panels were cut, and cleaned briefly by wiping with a papertowel moistened with isopropanol (IPA). After drying completely, thepanels were treated with the aerosol formulation sprayed from a distanceof 6″ for 3 seconds, with the panels in a horizontal position. Thepanels were then allowed to dry overnight, before testing.

The behavior of several water drops placed on the surface in ahorizontal position was tested, comparing treated and untreated surfacesas control. Surface behavior of several water droplets on the treatedsurfaces of the black acrylic plastic achieved a Roll-off test rating of2, while the untreated acrylic control exhibited a rating of 6, eventhough the water did not “wet” the surface of the untreated hydrophobicplastic. Surface behavior of several water droplets on the treatedsurfaces of the gray PVC plastic also achieved a Roll-off test rating of2, while the untreated PVC control exhibited a rating of 6. Theuniformity appearance ratings of both the treated acrylic test panel,and the treated PVC panel both gave a rating of 2 in comparison to theirrespective controls, thus providing a clear, invisible protectivecoating on the plastic surfaces.

To test the removability of the inventive treatment from these plastictreatments, the treated panels were wiped three times with a dry papertowel and retested as to their water roll-of properties. As with thewood paneling, behavior reverted to that observed on the originaluntreated panels. This further demonstrates the utility of the inventivetreatment compositions in providing non-durable protection to plasticsurfaces and materials. In addition, the easy removal of the treatmentwithout special chemical means is also demonstrated on these materials.

Textile Surface Modification

Example embodiments of the present invention were also tested for theirability to impart water roll-off properties to woven porous textilestypically used in the manufacture of clothing.

In this example, testing employed approximately 3″×5″ swatches of white(undyed and non-brightened) 100% cotton fabric, white 100% Nylon 6.6knit fabric, white 50-50 (%) cotton-polyester fabric, navy colored 100%Dacron 56 polyester texturized double knit heat set fabric dyed withDisperse Blue 167, Style No. TIC-720H and a dark blue colored 100% nylontexturized Nylon 6.6 knit fabric dyed with Acid Blue 113, Style No.TIC-314, all obtained from Textile Innovators Co., Windsor N.C.

The swatches were hung vertically and then treated with the sameinventive aerosol treatment composition as used above to treat plasticsubstrates. Treatment was accomplished by spraying the fabrics at adistance of 6 inches for about 3 seconds each, after which the swatcheswere allowed to dry overnight under ambient conditions. Three swatchesof each type were treated, and the results obtained from each replicatewere averaged.

The ability of the inventive treatment to produce water roll-off fromthe swatches was tested as follows. The swatches were placed on a hardflat surface which was inclined from the horizontal by about 20°. Usinga pipette, 6 drops of de-ionized water (approximately 200 microliterseach) were allowed to fall onto the swatch from a height of 6 inches. Inthis manner, the effect of the momentum of the falling drops on theirability to wet and penetrate the swatches is compared. Simple placementof the water drops onto fabric swatches can sometimes yield falsepositives, in that the water droplets tend to remain on the surface fora variable and non-reproducible period of time before finally wickinginto, or through the fabric. It was thus found that with some momentum,the force of the water drop impacting the surface of the fabric resultsin the fabric exhibiting its ultimate water wicking, and/or waterresistive nature more reproducibly for the purposes of test comparisons.

Fabrics with and without the inventive treatment were tested by theabove method, and a Repellency Score was assigned by visually observingand counting the number of repetitive water droplets impacting on thesame spot of the fabric required to produce wetting of the fabric atthat spot. The Repellency Score is the average number of water drops outof 18 (6 drops, three replicates of each swatch) that rolled off thefabric without sticking or wicking into the fabric. Thus, treatmentswith higher scores represent the ability of the fabric to resist wettingby water and repel water droplets. Fabric test results are presented inTable 15.

TABLE 15 Repellency Score⁽²⁾ Inventive Fabric Type (White) No TreatmentTreatment 100% Cotton 0  1 100% Nylon 0 18⁽¹⁾ Cotton Polyester blend 018⁽¹⁾ ⁽¹⁾No wetting observed after 18 consecutive drops. Testingstopped. ⁽²⁾Three replicates tested.

Results show that the inventive treatment compositions are mosteffective on porous textile materials having at least some syntheticfibers present, as performance on the 100% cotton (a natural, fairlyhydrophilic biopolymer) was marginal at best in repelling waterfollowing treatment.

The white fabrics were used to screen for any negative effects of theinventive treatments on yellowing or staining the fabrics. No yellowingor staining of the white fabrics was observed. The dark blue fabricswere used to observe whether use of the inventive treatments resulted inany appearance of visual fading, discoloration or greying of thefabrics. No fading, discoloration or greying effects were noted afterapplication to the dark fabrics. It was noted however that use of theinventive treatments on dark fabrics was observed to make them veryslightly darker in appearance when observed side by side with anuntreated fabric test swatch. Colorimetric measurements revealed thatuse of the inventive treatments yielded a Delta L value well below 3units, and with the dark fabrics a small negative Delta L value wasobserved, corresponding to the very slightly darker appearance noted byeye. This effect, though slight, is generally beneficially perceived asa color enhancement on darker fabrics, since fading due to wear,abrasion, washing, surface fiber damage and subsequent dye loss,otherwise produces changes in L resulting in larger positive Delta Lchanges, generally observable by eye when positive Delta L values exceeda value of greater than 5, the effect generally being attributed tooverall “fading.” Thus, the inventive treatment compositions tend toexhibit a slight anti-fading benefit on darker fabrics, and areessentially invisible on white and lighter-colored fabrics when appliedaccording to the methods of application described herein.

TABLE 16 Colorimetric Measurement⁽¹⁾ Fabric Type (Dyed) Delta L⁽²⁾ Deltaa Delta b 100% Nylon (Blue) −1.01 1.22 −0.60 100% Polyester (Navy) −0.490.61 −0.96 ⁽¹⁾Measurements taken with plain white backing, UV filterselected ⁽²⁾Colorimetric Lab values calculated from values before andafter treatment of same test swatch

These last few examples further demonstrate the utility of the inventivetreatment compositions to be used to treat a wide variety of both hard,non-porous materials such as plastics, wood, metal painted paneling,chrome and the like, as well as porous materials such as textiles, andto provide clear, protective coatings that repel water and dirt readilyfrom the surfaces of the treated materials, substrates and articlestreated according to the methods disclosed herein.

While the present invention has been shown and described in accordancewith practical and preferred embodiments thereof, it is recognized thatdepartures from the instant disclosure are contemplated within thespirit of the invention and, therefore, the scope of the inventionshould not be limited except as defined within the following claims asinterpreted under the doctrine of equivalents.

1. A method of forming a detachable and renewable protective coating ona receptive surface comprising the steps of: (a) applying a treatmentcomposition to said receptive surface, said treatment compositioncomprising a plurality of hydrophobically modified fumed silicaparticles colloidally dispersed in a volatile solvent; (b) allowing saidvolatile solvent to evaporate from said receptive surface; and (c)thereby depositing said protective coating on said receptive surface,wherein said protective coating provides dirt- and water-repellency tosaid receptive surface; wherein the protective coating comprises anon-smooth coating on the receptive surface at least after the treatmentcomposition has been applied to the receptive surface and hassubstantially dried or set, and wherein said non-smooth coating on thereceptive surface includes valleys and peaks and an average heightbetween the valleys and peaks of about 1-2500 nm.
 2. The method of claim1 wherein the treatment composition comprises a first and second set ofhydrophobically modified fumed silica colloidal particles, each of saidfirst and second sets of hydrophobically modified fumed silica colloidalparticles including a plurality of hydrophobically modified fumed silicacolloidal particles, each of said first and second sets ofhydrophobically modified fumed silica colloidal particles having anaverage particle size of hydrophobically modified fumed silica colloidalparticles, said first set of hydrophobically modified fumed silicacolloidal particles having an average particle size that is greater thansaid average size of said second set of hydrophobically modified fumedsilica colloidal particles, said composition including a greater numberof hydrophobically modified fumed silica colloidal particles in saidsecond set of colloidal particles than a number of hydrophobicallymodified fumed silica colloidal particles in said first set of colloidalparticles.
 3. The method of claim 2 wherein a size ratio of said averageparticle size of said first set of hydrophobically modified fumed silicacolloidal particles to said average particle size of said second set ofhydrophobically modified fumed silica colloidal particles is at leastabout 1.1:1.
 4. The method of claim 2 wherein a size ratio of saidaverage particle size of said first set of hydrophobically modifiedfumed silica colloidal particles to said average particle size of saidsecond set of hydrophobically modified fumed silica colloidal particlesis at least about 1.5-20:1.
 5. The method of claim 2 wherein a numberratio of said number colloidal particles of said second set ofhydrophobically modified fumed silica colloidal particles to said numberof particles of said first set of hydrophobically modified fumed silicacolloidal particles is at least about 2:1.
 6. The method of claim 2wherein a number ratio of said number of colloidal particles of saidsecond set of hydrophobically modified fumed silica colloidal particlesto said number of particles of said first set of hydrophobicallymodified fumed silica colloidal particles is about 10-1000:1.
 7. Themethod of claim 2 wherein said formed non-smooth surface on thesubstrate surface includes valleys and peaks and an average heightbetween the valley and peaks of about 2-100 nm.
 8. The method of claim 2wherein at least a portion of said colloidal particles in said first setof hydrophobically modified fumed silica colloidal particles, saidsecond set of hydrophobically modified fumed silica colloidal particles,or combinations thereof includes modified colloidal particles, saidmodified colloidal particles including at least one hydrocarbon chain.9. The method of claim 8 wherein at least one of said hydrocarbon chainsis an alkyl chain having 1-24 carbon atoms.
 10. The method of claim 1wherein said hydrophobically modified fumed silica particles have amedian particle size of between 100 and 4,000 nanometers.
 11. The methodof claim 1 wherein said detachable coating is substantially transparentand results in a change of less than 3.0 Delta E units to said receptivesurface measured before and after deposition of said coating.
 12. Themethod of claim 1 wherein said protective coating on said porous surfaceis substantially transparent and results in a change of less than 3.0Delta L units of said porous substrate after application of saidcoating.
 13. The method of claim 1 wherein said receptive surfacecomprises a non-porous substrate, porous substrate, and combinationsthereof.
 14. The method of claim 1 wherein said receptive surface isselected from the group consisting of automotive surfaces, householdinterior surfaces, household exterior surfaces, articles ofconstruction, and combinations thereof.
 15. The method of claim 1wherein said non-porous substrate is selected from the group consistingof metal, metal oxides, aluminum, anodized aluminum, painted substrates,stainless steel, chrome, clear-coated automotive surfaces, ellastomers,vinyl, plastics, polymers, sealed wood, laminates, composites, andcombinations thereof.
 16. The method of claim 1 wherein said poroussubstrate is selected from the group consisting of fibers, textiles,non-wovens, foam substrates, cloth, clothing, leather, upholstery,carpet, curtains, marble, granite, grout, mortar, concrete, spackling,plaster, adobe, stucco, brick, unglazed tile, tile, unglazed porcelain,porcelain, clay, wallpaper, cardboard, paper, wood, and combinationsthereof.
 17. The method of either claim 1 wherein said coating furtherexhibits a Durability Duration value of greater than or equal to 15seconds.
 18. A treatment composition for forming a detachable andrenewable protective coating on a receptive surface comprising: (i) 0.05to 5.0 percent by weight of a plurality of hydrophobically modifiedfumed silica particles having a median particle size of between 100 and4,000 nanometers; (ii) 99.95 to 5 percent by weight of a volatilesolvent; (iii) optionally, 0.001 to 5 percent by weight of a suspendingagent; (iv) optionally, 0.001 to 5 percent by weight of a functionaladjunct; and (v) optionally, in balance to 100 percent by weight ifpresent, a propellant; wherein said treatment composition when appliedto said receptive surface deposits said protective coating on saidreceptive surface, wherein said protective coating provides dirt- andwater-repellency to said receptive surface; and wherein the protectivecoating comprises a non-smooth coating on the receptive surface at leastafter the treatment composition has been applied to the receptivesurface and has substantially dried or set, and wherein said non-smoothcoating on the receptive surface includes valleys and peaks and anaverage height between the valleys and peaks of about 1-2500 nm.
 19. Thetreatment composition of claim 18 which comprises a first and second setof hydrophobically modified fumed silica colloidal particles, each ofsaid first and second sets of hydrophobically modified fumed silicacolloidal particles including a plurality of hydrophobically modifiedfumed silica colloidal particles, each of said first and second sets ofhydrophobically modified fumed silica colloidal particles having anaverage particle size of hydrophobically modified fumed silica colloidalparticles, said first set of hydrophobically modified fumed silicacolloidal particles having an average particle size that is greater thansaid average size of said second set of hydrophobically modified fumedsilica colloidal particles, said composition including a greater numberof hydrophobically modified fumed silica colloidal particles in saidsecond set of colloidal particles than a number of hydrophobicallymodified fumed silica colloidal particles in said first set of colloidalparticles.
 20. The treatment composition of claim 18, wherein saidsuspending agent is selected from the group consisting of polymers,surfactants, and mixtures thereof.
 21. The treatment composition ofclaim 18, wherein said functional adjunct is selected from the groupconsisting of ultraviolet light absorbers, ultraviolet light blockers,free-radical scavengers, fluorescent whitening agents, colorants, dyes,pigments, photoactive particles, color changing dyes, color fading dyes,bleaching agents, fixative agents, spreading agents, evaporationmodifiers, azeotropic cosolvents, stabilizers, perfume, fragrance, odorcontrol agents, anti-static agents, thickeners, and mixtures thereof.22. The treatment composition of claim 18, wherein said receptivesurface comprises a non-porous substrate, porous substrate, andcombinations thereof; wherein said detachable coating on said non-poroussubstrate results in a change of less than 3.0 Delta E units of saidsurface of said non-porous substrate after application of said coating;and wherein said protective coating on said porous substrate results ina change of less than either (a) 3.0 Delta E units and/or (b) 3.0 DeltaL units of said surface of said porous substrate after application ofsaid coating.
 23. A treatment system for applying and forming adetachable and renewable protective coating on a receptive surfacecomprising: (a) an applicator; and (b) a treatment composition forforming a protective coating on said receptive surface comprising: i.0.05 to 5.0 percent by weight of a plurality of hydrophobically modifiedfumed silica particles having a median particle size of between 100 and4,000 nanometers; ii. 99.95 to 5 percent by weight of a volatilesolvent; iii. optionally, 0.001 to 5 percent by weight of a suspendingagent; iv. optionally, 0.001 to 5 percent by weight of a functionaladjunct; and v. optionally, in balance to 100 percent by weight ifpresent, a propellant; (c) optionally, a drying article; wherein saidtreatment composition when applied to said receptive surface depositssaid protective coating on said receptive surface, wherein saidprotective coating provides dirt- and water-repellency to said receptivesurface; and wherein the protective coating comprises a non-smoothcoating on the receptive surface at least after the treatmentcomposition has been applied to the receptive surface and hassubstantially dried or set, and wherein said non-smooth coating on thereceptive surface includes valleys and peaks and an average heightbetween the valleys and peaks of about 1-2500 nm.
 24. The treatmentsystem of claim 23 wherein the treatment composition comprises a firstand second set of hydrophobically modified fumed silica colloidalparticles, each of said first and second sets of hydrophobicallymodified fumed silica colloidal particles including a plurality ofhydrophobically modified fumed silica colloidal particles, each of saidfirst and second sets of hydrophobically modified fumed silica colloidalparticles having an average particle size of hydrophobically modifiedfumed silica colloidal particles, said first set of hydrophobicallymodified fumed silica colloidal particles having an average particlesize that is greater than said average size of said second set ofhydrophobically modified fumed silica colloidal particles, saidcomposition including a greater number of hydrophobically modified fumedsilica colloidal particles in said second set of colloidal particlesthan a number of hydrophobically modified fumed silica colloidalparticles in said first set of colloidal particles.
 25. The treatmentsystem of claim 23 wherein said receptive surface is a non-poroussubstrate and/or a porous substrate, wherein said coating issubstantially transparent and results in a change of less than 3.0 DeltaE units to said non-porous substrate and/or results in a change of lessthan 3.0 Delta L units to said porous substrate, wherein the surface ismeasured before and after deposition of said coating
 26. The treatmentsystem of claim 23 wherein said applicator comprises a device capable ofdispensing said treatment composition in the form of a fine spraycomprising a plurality of liquid droplets, and capable of directing saidplurality of liquid droplets onto said receptive surface.
 27. Thetreatment system of claim 23 wherein said applicator comprises apressurized or a non-pressurized delivery device.
 28. The treatmentsystem of claim 23 wherein said drying article is selected from anabsorbent article, a drying device, and combinations thereof; whereinsaid absorbent article is selected from a woven, non-woven, sponge,polymeric foam, microfiber, paper towel, paper pad, paper towel, cloth,and combinations thereof; wherein said drying device is selected from acompressed gas source, infrared heat generating device, forced airdevice, battery powered fan, and combinations thereof.
 29. A method offorming a detachable and renewable protective coating on a receptivesurface comprising the steps of: (a) applying a treatment composition tosaid receptive surface, said treatment composition comprising aplurality of hydrophobically modified fumed silica particles colloidallydispersed in a volatile solvent; (b) allowing said volatile solvent toevaporate from said receptive surface; and (c) thereby depositing saidprotective coating on said receptive surface, wherein said protectivecoating provides dirt- and water-repellency to said receptive surface;wherein the protective coating comprises a non-smooth coating on thereceptive surface at least after the treatment composition has beenapplied to the receptive surface and has substantially dried or set, andwherein said non-smooth coating on the receptive surface includesvalleys and peaks and an average height between the valleys and peaks ofabout 1-2500 nm.
 30. The method of claim 29 wherein the treatmentcomposition comprises a first and second set of hydrophobically modifiedfumed silica colloidal particles, each of said first and second sets ofhydrophobically modified fumed silica colloidal particles including aplurality of hydrophobically modified fumed silica colloidal particles,each of said first and second sets of hydrophobically modified fumedsilica colloidal particles having an average particle size ofhydrophobically modified fumed silica colloidal particles, said firstset of hydrophobically modified fumed silica colloidal particles havingan average particle size that is greater than said average size of saidsecond set of hydrophobically modified fumed silica colloidal particles,said composition including a greater number of hydrophobically modifiedfumed silica colloidal particles in said second set of colloidalparticles than a number of hydrophobically modified fumed silicacolloidal particles in said first set of colloidal particles.
 31. Themethod of claim 29 wherein said detachable coating is substantiallytransparent and results in a change of less than 250 Delta Haze units tosaid receptive surface measured before and after deposition of saidcoating, as measured by the Chrome Test
 32. A treatment composition forforming a detachable and renewable protective coating on a receptivesurface comprising: (a) 0.05 to 5.0 percent by weight of a plurality ofhydrophobically modified fumed silica particles having a median particlesize of between 100 and 4,000 nanometers; (b) 99.95 to 5 percent byweight of a volatile solvent; (c) optionally, 0.001 to 5 percent byweight of a suspending agent; (d) optionally, 0.001 to 5 percent byweight of a functional adjunct; and (e) optionally, in balance to 100percent by weight if present, a propellant; wherein said treatmentcomposition when applied to said receptive surface deposits saidprotective coating on said receptive surface, wherein said protectivecoating provides dirt- and water-repellency to said receptive surface;wherein the protective coating comprises a non-smooth coating on thereceptive surface at least after the treatment composition has beenapplied to the receptive surface and has substantially dried or set, andwherein said non-smooth coating on the receptive surface includesvalleys and peaks and an average height between the valleys and peaks ofabout 1-2500 nm.
 33. The treatment composition of claim 32 whichcomprises a first and second set of hydrophobically modified fumedsilica colloidal particles, each of said first and second sets ofhydrophobically modified fumed silica colloidal particles including aplurality of hydrophobically modified fumed silica colloidal particles,each of said first and second sets of hydrophobically modified fumedsilica colloidal particles having an average particle size ofhydrophobically modified fumed silica colloidal particles, said firstset of hydrophobically modified fumed silica colloidal particles havingan average particle size that is greater than said average size of saidsecond set of hydrophobically modified fumed silica colloidal particles,said composition including a greater number of hydrophobically modifiedfumed silica colloidal particles in said second set of colloidalparticles than a number of hydrophobically modified fumed silicacolloidal particles in said first set of colloidal particles.
 34. Thetreatment composition of claim 32 wherein said coating is substantiallytransparent and results in a change of less than 250 Delta Haze units tosaid receptive surface measured before and after deposition of saidcoating, as measured by the Chrome Test.
 35. A treated articlecomprising: (1) a substrate bearing at least one receptive surface; and(2) a detachable and renewable protective coating deposited onto saidreceptive surface, wherein said protective coating is formed by the useof a treatment composition comprising: (a) 0.05 to 5.0 percent by weightof a plurality of hydrophobically modified fumed silica particles havinga median particle size of between 100 and 4,000 nanometers; (b) 99.95 to5 percent by weight of a volatile solvent; (c) optionally, 0.001 to 5percent by weight of a suspending agent; (d) optionally, 0.001 to 5percent by weight of a functional adjunct; and (e) optionally, inbalance to 100 percent by weight if present, a propellant; wherein theprotective coating comprises a non-smooth coating on the receptivesurface at least after the treatment composition has been applied to thereceptive surface and has substantially dried or set, and wherein saidnon-smooth coating on the receptive surface includes valleys and peaksand an average height between the valleys and peaks of about 1-2500 nm.36. The treated article of claim 35 wherein the treatment compositioncomprises a first and second set of hydrophobically modified fumedsilica colloidal particles, each of said first and second sets ofhydrophobically modified fumed silica colloidal particles including aplurality of hydrophobically modified fumed silica colloidal particles,each of said first and second sets of hydrophobically modified fumedsilica colloidal particles having an average particle size ofhydrophobically modified fumed silica colloidal particles, said firstset of hydrophobically modified fumed silica colloidal particles havingan average particle size that is greater than said average size of saidsecond set of hydrophobically modified fumed silica colloidal particles,said composition including a greater number of hydrophobically modifiedfumed silica colloidal particles in said second set of colloidalparticles than a number of hydrophobically modified fumed silicacolloidal particles in said first set of colloidal particles.
 37. Aprotective coating on a receptive surface that is formed by the use of atreatment composition comprising: (a) 0.05 to 5.0 percent by weight of aplurality of hydrophobically modified fumed silica particles having amedian particle size of between 100 and 4,000 nanometers; (b) 99.95 to 5percent by weight of a volatile solvent; (c) optionally, 0.001 to 5percent by weight of a suspending agent; (d) optionally, 0.001 to 5percent by weight of a functional adjunct; and (e) optionally, inbalance to 100 percent by weight if present, a propellant; wherein theprotective coating comprises a non-smooth coating on the receptivesurface at least after the treatment composition has been applied to thereceptive surface and has substantially dried or set, and wherein saidnon-smooth coating on the receptive surface includes valleys and peaksand an average height between the valleys and peaks of about 1-2500 nm.38. The protective coating of claim 37 wherein the treatment compositioncomprises a first and second set of hydrophobically modified fumedsilica colloidal particles, each of said first and second sets ofhydrophobically modified fumed silica colloidal particles including aplurality of hydrophobically modified fumed silica colloidal particles,each of said first and second sets of hydrophobically modified fumedsilica colloidal particles having an average particle size ofhydrophobically modified fumed silica colloidal particles, said firstset of hydrophobically modified fumed silica colloidal particles havingan average particle size that is greater than said average size of saidsecond set of hydrophobically modified fumed silica colloidal particles,said composition including a greater number of hydrophobically modifiedfumed silica colloidal particles in said second set of colloidalparticles than a number of hydrophobically modified fumed silicacolloidal particles in said first set of colloidal particles.